Direct Observation of Non-covalent Complexes for Phosphorylated Flavonoid-protein Interaction by ESI

Diethyl flavon-7-yl phosphate was synthesized by modified Atheron-Todd reaction. The result of ESI shows that the phosphated flavonoids possess stronger binding affinities toward proteins such as myoglobin, insulin and lysozyme and are easier to form the non-covalent complexes with them.     

Time-resolved synchrotron X-ray study of crystalline phase transition in poly(aryl ether ketone ketone) containing alternated terephthalic/isophthalic moieties

Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.     

三种胺羧配合物的113Cd NMR研究

该文对Cd-HEDTA(N-(2-羟基乙基)乙二胺-N',N',N'-三乙酸),Cd-PDTA(1,2丙二胺四乙酸)和Cd-DTPA(二乙三胺五乙酸)的¹¹³Cd NMR谱和自旋晶格弛豫时间T₁,及NOE因子进行了研究.结果表明,Cd-HEDTA和Cd-PDTA结构与Cd-EDTA类似,Cd-PDTA双线归因于其可能的两种异构体.Cd-DTPA大的化学位移表明其具有七配位的五角双锥结构.在这种结构中DTPA可用三个氮原子参加配位.对¹¹³Cd自旋晶格弛豫时间分析表明,Cd-DTPA配合物中质子偶极作用机理的贡献较大,这归因于Cd DTPA有更多的乙酸根亚甲基质子参与偶极作用.     

Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Olefinic-ester cyclizations using Takai-Utimoto reduced titanium alkylidenes

The scope and limitations of the Takai-Utimoto reagent to induce the cyclization of olefinic-esters is described. Critical is the steric environment about both the ester and the olefin. Mechanistically, these results support the hypothesis that cyclized product comes from an olefin metathesis, carbonyl-olefination sequence.     

Synthesis,dynamic light scattering,and luminescence properties of copolymers containing iridium(III) bisterpyridine in the side chain

Supramolecular block‐random copolymers containing [Ir(terpy)₂]³⁺ in the side chain were synthesized via postfunctionalization of a P(S‐b‐AC_terpy) block copolymer. Absorbance and emission spectra compared to a model compound show that the polymer backbone has a minor effect on the polymer absorbance but produces a larger shift for the phosphorescence signals to higher wavelength. Dynamic light scattering of the metal complex containing copolymer studied in various solvents showed monomodal aggregation with decreasing aggregate size as the solvent dielectric constant increased. The copolymer precursor P(S‐b‐AC_terpy) shows multimodal aggregation in different solvents with the major population consisting of single chains. This difference in behavior between the two polymers is attributed to the electrolytic nature of the complex and the amphiphilicity induced by the charged metal complex. Supramolecular copolymers like these will continue to have interesting self‐organizational properties and may find applications in multicomponent systems for photoinduced charge separation processes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1109–1121, 2007     

Synthesis and characterization of highly fluorescent europium functionalized β-diketonate complexes

Several functionalized β-diketones and their europium complexes have been synthesized and characterized. The UV-Vis absorption, photoluminescent spectra, thermal and electrochemical properties of these complexes were investigated. The thermal analysis shows that the complexes have good thermal stability. By introducing the number of extended phenyl rings we succeeded in obtaining europium complexes with extremely high photoluminescent quantum yield (PLQY) in solution due to strong site isolation effect.     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

Trovacenchemie. 13 [1] Weg und Irrweg zu Di([5]trovacenyl)keton

Trovacene Chemistry. 13 [1] On Being Lead and Mislead in the Synthesis of Di([5]trovacenyl)ketone Di([5]trovacenyl)ketone ( 3¨ ) has been prepared from lithio‐[5]trovacene and dimethylcarbamoyl chloride and studied by X‐ray diffraction, cyclic voltammetry, magnetic susceptometry and EPR spectroscopy. Slight variation of the synthetic protocol affords an unusual trinuclear complex 5 ? that is also fully characterized. Spin‐spin exchange interaction is smaller in 3¨ than in 1,1‐di([5]trovacenylethene ( 2¨ ), which differs from 3¨ by a replacement of O for CH₂. The novel trinuclear complex 5 ? , however, displays exchange coupling very similar to that observed in 1‐methoxy‐2,5,6‐tri([5]trovacenyl)benzene ( 7 ? ). In both cases, an unsymmetrical triangular arrangement of S = 1/2 centers is encountered. These findings are discussed in terms of the nature of the respective spacers.