Spectroscopic studies on 2,3,4,5-tetraphenylpyrylium salts with and without silver (I)-bridged structures

Two novel phenylated pyrylium compounds, silver (I)-bridged 2,3,4,5-tetraphenylpyrylium perchlorate (P1) and its silver (I)-free pyrylium ligand (P2) were prepared from 1,2,3,4-tetraphenylcyclopentadiene to examine their spectroscopic behaviors. The UV/vis absorption and fluorescent emission spectra of P1 and P2, measured in three solvents (acetonitrile, dichloromethane and toluene), reveal that the photophysical behaviors are closely related to silver (I) fragment, and strongly dependent on solvent polarity. In polar acetonitrile, P1 displays longer absorption wavelength and much lower fluorescent emission intensity than P2, although they exhibit much similarity in shape. In contrast, in nonpolar toluene, while P2 shows an apparent absorption band at 338 nm, P1 displays a tail-like line without absorption band observed. All the spectra obtained indicate a better coplanarity and a stronger intra-molecular charge transfer in P1 due to the effect of silver (I) fragment. Additionally, the 1H NMR spectra of P1 and P2, which were recorded under the same conditions, indicate that the silver (I) fragment reinforces pyrylium ring's capacity to localize the formal positive charge within the heterocyclic ring.     

Construction of a 2,6-difunctionalized 2-methyl-2H-1-benzopyran library by using a solid-phase synthesis protocol

[reaction: see text] A library containing 1200 analogues of 2,6-difunctionalized 2-methyl-2H-1-benzopyran was constructed by using a solid-phase synthesis protocol. Polymer-bound 6-amido-, 6-sulfonamido-, and 6-uredo-functionalized 2-hydroxymethyl-2-methylbenzopyrans 10 were prepared as part of a first-generation diversification step by employing reactions of respective acid halides, sulfonyl chlorides, and isocyanates with the amine precursor 7. Transformations of the resin-bound intermediates 10 by reactions with alkyl and acid halides were then used to produce a diverse series of 2,6-difunctionalized 2-methyl-2H-1-benzopyran analogues 12 and 14.     

Electrophoretic deposition of titanate nanotube films with extremely large wetting contrast

A facile electrophoretic deposition (EPD) process has been developed to prepare thin films consisting of titanate nanotubes (TNTs) that were synthesized by a hydrothermal approach. Such an EPD process offers easy control in the film thickness and the adhesion to the substrate was found to be strong. The chemical composition and structure of the products have been characterized by XRD, HRTEM, and FESEM. It was found that the functionalization of TNTs plays a key role on the electrolyte stability and the formation of a uniform TNT film with good adhesion. The as-prepared TNT films show exceptional superhydrophilic behavior with ultra-fast spreading, while it converts to superhydrophobicity yet with strong adhesion after 1H,1H,2H,2H-perfluorooctyl-triethoxysilane modification. This study provides an interesting method to prepare films with extremely high wettability contrast that are useful for producing different types of functional materials.     

Evaluation of separation quality in two-dimensional hyphenated chromatography

In this paper, a novel criterion named the overlap index (OVI) has been proposed to evaluate the separation quality in two-dimensional hyphenated chromatography. This criterion, which is obtained from the maximum value of the Gram determinant constructed by the key spectra, can reveal the degree of two-dimensional hyphenated chromatographic separation. The key spectra are selected based on the so-called D-optimal criterion. According to its geometrical sense meaning the volume spanned by the constructed vectors, OVI criterion can practically reflect the overlap degree of chromatographic peaks. The OVI criterion is further interpreted by comparing the resolution of two-dimensional data into pure chromatograms and spectra. The successful application of this OVI criterion to both of simulated two-dimensional hyphenated data and the real case in analyzing the six reference phenolic compounds from Ginkgo biloba L-leaves shows its reliability and practicality.     

Two Novel Poly-Oxygen Bipyridine Alkaloids from Speranskia tuberculata

In a previous paper' we reported two optically active pyridine-2, 6 (l H. 3H)-dionealkatoids speranskalines A and B from SPeranskia luberculala (Bge.) (Euphorbiaceae)We report here the isolation and structural elucidation of two novel poly-oxygenbipyridine alkaloids named speranculatines A (l) and B (2) from this plant.The acetone (or methanol) extract of the air-dried whole plants of .q. IllhelT.lllaluwas subjected to column chromatography on St gel to afford a fraction. whichdemonstrate…     

p‐Methoxy­benz­aldehyde benzoyl­hydrazone monohydrate

The crystal structure of the title compound, C₁₅H₁₄N₂O₂·H₂O, is in the keto tautomeric form and the configuration at the azomethine C=N double bond is E. The mol­ecule is non‐planar, with a dihedral angle of 27.3 (1)° between the aromatic rings. The crystal structure is stabilized by extensive hydrogen bonding involving the water mol­ecule and hydrazone moiety.     

Aggregation behavior of block polyethers with branched structure at air/water surface

The block polyethers with various branch structure, such as TEPA[(PO)₃₆(EO)₁₀₀]₇, TEPA[(PO)₃₆(EO)₁₀₀(PO)₃₆]₇, and TEPA[(PO)₃₆(EO)₁₀₀(PO)₅₆]₇ were synthesized. Moreover, the aggregation behavior was investigated via the measurements of equilibrium surface tension, dynamic surface tension, and surface dilational viscoelasticity, in order to probe the effect of the block structure on the property of the branched block polyethers. The surface tension results show that the efficiency and effectiveness of the block polyethers to lower surface tension increase with the increase of the PO group numbers. The maximum surface excess concentration (Γ_max) values and the minimum occupied area per molecule at the air/water interface (A_min) values of the branched block polyethers obtained from Gibbs adsorption equations increase and decrease with the increases of the PO group numbers, respectively. The dynamic parameters n and t^* representing the diffusion speed of the polyether molecules from bulky solution to the subsurface and from the subsurface to the air/water surface are obtained according to the equation proposed by Rosen. The results show that the n values firstly increase and then decrease and t^* values decrease with the increase of the polyether concentrations. The results of surface dilational viscoelasticity show that the dilational modulus of TEPA[(PO)₃₆(EO)₁₀₀(PO)₅₆]₇ is the largest among the three block copolymers at the low concentration (<1 mg L⁻¹) but that of TEPA[(PO)₃₆(EO)₁₀₀]₇ is the largest at the high concentration (>1 mg L⁻¹).     

An economic evaluation model of supply chain flexibility

With the advent of the supply chain management concepts, business communities have been realizing that being competitive as a single company is no longer adequate; instead, competitiveness requires consideration of all channels in the supply chain. Despite its importance, the availability of the literature addressing supply chain flexibility is still limited to date. Although relationships between various types of flexibilities have been established, the degree to which one type of flexibility affects the other types and the system performance remains to be investigated. In particular, there is a lack of rigorous analytical models elucidating the relationships between the degree of flexibility in a system and the system level of performance. In this paper, a supply chain flexibility model is developed comprising labor flexibility, machine flexibility, routing flexibility, and information technology, with total system flexibility measured by an economic index. Outputs from the model can assist in making suitable production decisions to produce multiple products under an uncertain environment. Example solutions are given. This paper can help economic evaluation when supply chain flexibility and the factors affecting flexibility are to be improved. It can also assist in making supply chain flexibility-promotion decisions.     

Identification of metabolites of Danggui Buxue Tang in rat urine by liquid chromatography coupled with electrospray ionization time‐of‐flight mass spectrometry

A method coupling liquid chromatography with electrospray ionization time‐of‐flight mass spectrometry (LC/ESI‐TOF/MS) has been developed for rapid and sensitive analysis of rat urinary metabolite profile of Danggui Buxue Tang (DBT), a well‐known Chinese herbal formula. After oral administration of DBT, urine samples were collected during 0–24 h, and then pretreated by solid‐phase extraction. A total of 68 compounds including 13 parent compounds and 55 metabolites were detected in the drug‐containing urines compared with blank urines. The total analytical time was less than 20 min. Metabolites of DBT were identified using dynamic adjustment of the fragmentor voltage to produce structure‐relevant fragment ions. By using this approach, the mass accuracy of precursor and fragment ions was typically within ±5 ppm of the theoretical values, and enabled the identification of 43 metabolites including 27 isoflavanoid and 16 phthalide metabolites. Our results indicated that glucuronidation and sulfation were the major metabolic pathways of isoflavonoids, while glutathione conjugation, glucuronidation and sulfation were the main metabolic pathways of phthalides. No saponin‐related metabolites were detected. The results of the present study provided important structural information relating to the metabolism of DBT. Furthermore, this work demonstrated the potential of the LC/ESI‐TOF/MS approach for identification of metabolites from Chinese herbal medicines in urine. Copyright © 2009 John Wiley & Sons, Ltd.