Home About us Contact
|
Home About us Contact | ||
|
|
||
Terminal Units (terminal + unit)
Selected AbstractsReversed-phase HPLC-ESI/MS analysis of birch leaf proanthocyanidins after their acidic degradation in the presence of nucleophilesPHYTOCHEMICAL ANALYSIS, Issue 5 2007Maarit Karonen Abstract Mountain birch leaves contain large amounts of structurally variable polymeric proanthocyanidins. Their isolation procedure was enhanced by the addition of liquid,liquid extractions prior to column chromatography over Sephadex LH-20. Isolated polymeric proanthocyanidins were depolymerised by acid-catalysis in the presence of benzyl mercaptan or phloroglucinol in order to study their composition. The resulting degradation products, flavan-3-ols and flavan-3-ol adducts, were analysed with reversed-phase high-performance liquid chromatography using UV photodiode array detection for quantification and electrospray ionisation mass spectrometry for identification. The results showed that polymeric proanthocyanidins contained (epi)gallocatechins and (epi)catechins as the extension units and, mainly, (+)-catechin as the terminal unit. The mean degree of polymerisation was found to be 26 based on thiolysis and 31 based on phloroglucinol degradation. Copyright © 2007 John Wiley & Sons, Ltd. [source] Biochemical universality of living matter and its metabolic implicationsFUNCTIONAL ECOLOGY, Issue 4 2005A. M. MAKARIEVA Summary 1Recent discussions of metabolic scaling laws focus on the model of West, Brown & Enquist (WBE). The core assumptions of the WBE model are the size-invariance of terminal units at which energy is consumed by living matter and the size-invariance of the rate of energy supply to these units. Both assumptions are direct consequences of the biochemical universality of living matter. However, the second assumption contradicts the central prediction of the WBE model that mass-specific metabolic rate q should decrease with body mass with a scaling exponent µ = ,1/4, thus making the model logically inconsistent. 2Examination of evidence interpreted by WBE and colleagues in favour of a universal µ = ,1/4 across 15 and more orders of magnitude range in body mass reveals that this value resulted from methodological errors in data assortment and analysis. 3Instead, the available evidence is shown to be consistent with the existence of a size-independent mean value of mass-specific metabolic rate common to most taxa. Plotted together, q -values of non-growing unicells, insects and mammals in the basal state yield µ , 0. Estimated field metabolic rates of bacteria and vertebrates are also size-independent. 4Standard mass-specific metabolic rates of most unicells, insects and mammals studied are confined between 1 and 10 W kg,1. Plant leaves respire at similar rates. This suggests the existence of a metabolic optimum for living matter. With growing body size and diminishing surface-to-volume ratio organisms have to change their physiology and perfect their distribution networks to keep their q in the vicinity of the optimum. [source] Dipole moments of polyenic oligomeric systems.JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 9 2005Part II, allenes, molecular organic wire resistivities: polyacetylenes, polyynes Abstract Polyacetylenic, allenic and polyynic molecular wire series, containing electron-donor (D) and electron-acceptor (A) groups as two terminal units of the oligomeric bridge (D,wire,A), can be well described by means of a one-dimensional conduction model, which considers a scattering process of electrons through the charge-transfer conduction bridge. The conduction constants (,i) of the oligomeric structures of the three molecular series under study were determined from the functional dependence between the dipole moment of the oligomers (,n) and the ,-molecular orbital bridge length (L). According to our one-dimensional molecular organic wire model: where ,o is the dipolar moment of the first compound of the oligomeric series without a bridge unit (n,=,0) and ,, is a limit value for L,,,,. By means of the Landauer theoretical expression for the conductance of a metallic one-dimensional conductor and our molecular wire conduction constants (,i), we determined the intrinsic resistivities associated with the molecular resistances of these oligomeric wires. Using this approach we determined, for the first time, the linear and non-linear contributions to the net molecular resistivity. The order of magnitudes of the linear resistivities determined in these oligomeric systems agrees very well with the expected results of experimental measurements for macroscopic wires. Copyright © 2005 John Wiley & Sons, Ltd. [source] Hydroxyl-terminated hyperbranched aromatic poly(ether-ester)s: Synthesis, characterization, end-group modification, and optical propertiesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2008Thiyagarajan Shanmugam Abstract Novel AB2 -type monomers such as 3,5-bis(4-methylolphenoxy)benzoic acid (monomer 1), methyl 3,5-bis(4-methylolphenoxy) benzoate (monomer 2), and 3,5-bis(4-methylolphenoxy)benzoyl chloride (monomer 3) were synthesized. Solution polymerization and melt self-polycondensation of these monomers yielded hydroxyl-terminated hyperbranched aromatic poly(ether-ester)s. The structure of these polymers was established using FTIR and 1H NMR spectroscopy. The molecular weights (Mw) of the polymers were found to vary from 2.0 × 103 to 1.49 × 104 depending on the polymerization techniques and the experimental conditions used. Suitable model compounds that mimic exactly the dendritic, linear, and terminal units present in the hyperbranched polymer were synthesized for the calculation of degree of branching (DB) and the values ranged from 52 to 93%. The thermal stability of the polymers was evaluated by thermogravimetric analysis, which showed no virtual weight loss up to 200 °C. The inherent viscosities of the polymers in DMF ranged from 0.010 to 0.120 dL/g. End-group modification of the hyperbranched polymer was carried out with phenyl isocyanate, 4-(decyloxy)benzoic acid and methyl red dye. The end-capping groups were found to change the thermal properties of the polymers such as Tg. The optical properties of hyperbranched polymer and the dye-capped hyperbranched polymer were investigated using ultraviolet-absorption and fluorescence spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5414,5430, 2008 [source] Isolation and Characterisation of Procyanidins from Rumex obtusifoliusPHYTOCHEMICAL ANALYSIS, Issue 3 2007Paul Spencer Abstract An acetone:water (7:3) extract obtained from the leaves of Rumex obtusifolius was fractionated into procyanidin oligomer and polymer fractions using a linear gradient and a simple step method on Sephadex LH-20. The chemical characteristics of the procyanidin fractions were studied by 13C-NMR spectroscopy, acid-catalysed degradation in the presence of benzyl mercaptan, matrix-assisted laser desorption/ionisation time-of-flight (MALDI-TOF) MS and electrospray ionisation (ESI) MS. The 13C-NMR showed that the polymer fraction consisted predominantly of procyanidin polymers, some with galloyl groups attached. The thiolysis reaction products indicated a mean degree of polymerisation (DP) of 4.3 for the step method, and a range of 2.3,8.2 mean DP for the gradient fractionation, with epicatechin as the most abundant flavan-3-ol extension unit, while the terminal units consisted of equal proportions of catechin, epicatechin and epicatechin gallate. Singly charged ions observed in MALDI-TOF/MS showed a range of oligomeric procyanidins and their polygalloyl derivatives. These species (in the range DP 2,7) were also observed by ESI/MS but the spectra were more complex due to overlapping multiply charged ions. Isolation of oligomers from the Sephadex LH-20 fraction by chromatography on polyamide and C18 yielded B1, B2, B3 and B7 dimers, an A-type trimer and a B2 3,3,- O -digallate. Copyright © 2007 John Wiley & Sons, Ltd. [source] Synthesis and polymerization reactions of cyclic imino ethers.POLYMER ENGINEERING & SCIENCE, Issue 8 2007To study the effect of nonequal reactivity of B units in ABx monomers, two novel monomers for synthesis of hyperbranched polymers of the polyaddition type, namely 2-(2,5-dihydroxyphenyl)-2-oxazoline (2a) and 2-(2,4-dihydroxyphenyl)-2-oxazoline (2b) were prepared and characterized. Both monomers have one free phenolic group and one hydrogen-bonded phenolic group with the difference in chemical shift more than 2 ppm. Both monomers undergo thermally initiated polymerization in bulk and in solution at the temperature 220°C during 1 h in bulk and 24 h in solution of 1-chloronaphthalene. Products are white powders with degree of polymerization 17 and 13 for the respective polymer 3a and 3b. The degree of branching is 0.37 and 0.3 for the respective polymer. The structure of polymers is in agreement with the structure, which was expected from the structure of monomers and consists of linear, dendritic, and terminal units. POLYM. ENG. SCI., 47:1272,1280, 2007. © 2007 Society of Plastics Engineers [source] Do Trinuclear Triplesalen Complexes Exhibit Cooperative Effects?CHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2010Characterization, Enantioselective Catalytic Sulfoxidation by Chiral Trinuclear FeIII Triplesalen Complexes, Synthesis Abstract The chiral triplesalen ligand H6chand provides three chiral salen ligand compartments in a meta -phenylene arrangement by a phloroglucinol backbone. The two diastereomeric versions H6chandRR and H6chandrac have been used to synthesize the enantiomerically pure chiral complex [(FeCl)3(chandRR)] (3RR) and the racemic complex [(FeCl)3(chandrac)] (3rac). The molecular structure of the free ligand H6chandrac exhibits at the terminal donor sides the O-protonated phenol,imine tautomer and at the central donor sides the N-protonated keto,enamine tautomer. The trinuclear complexes are comprised of five-coordinate square-pyramidal FeIII ions with a chloride at the axial positions. The crystal structure of 3rac exhibits collinear chiral channels of ,11,Å in diameter making up 33.6,% of the volume of the crystals, whereas the crystal structure of 3RR exhibits voids of 560,Å3. Mössbauer spectroscopy demonstrates the presence of FeIII high-spin ions. UV/Vis spectroscopy is in accordance with a large delocalized system in the central backbone evidenced by strong low-energy shifts of the imine ,,,* transitions relative to that of the terminal units. Magnetic measurements reveal weak intramolecular exchange interactions but strong magnetic anisotropies of the FeIII ions. Complexes 3rac and 3RR are good catalysts for the sulfoxidation of sulfides providing very good yields and high selectivities with 3RR being enantioselective. A comparison of 3RR and [FeCl(salen,)] provides higher yields and selectivities but lower enantiomeric excess values (ee values) for 3RR relative to [FeCl(salen,)]. The low ee values of 3RR appeared to be connected to a strong ligand folding in 3RR, opening access to the catalytically active high-valent Fe,O species. The higher selectivity is assigned to a cooperative stabilization of the catalytically active high-valent Fe,O species through the phloroglucinol backbone in the trinuclear complexes. [source] | |||||||||||||