Rapid Prediction of the Hydrogen Bond Cooperativity in N‐methylacetamide Chains

A method is proposed to rapidly predict the hydrogen bond cooperativity in N‐methylacetamide chains. The parameters needed are obtained from the fittings to the hydrogen bonding energies in the formamide chains containing 2 to 8 monomeric units. The scheme is then used to calculate the individual hydrogen bonding energies in N‐methylacetamide chains containing 2 to 7 monomeric units. The cooperativity predicted is in good agreement with those obtained from MP2/6‐31+G** calculations by including the BSSE correction. Our scheme is further employed to predict the individual hydrogen bonding energies in larger N‐methylacetamide chains containing up to 200 monomeric N‐methylacetamide units, to which the MP2 method cannot be applied. Based on our scheme, a cooperative effect of over 170 % of the dimer hydrogen bonding energy in long N‐methylacetamide chains is predicted. The method is also applied to heterogeneous chains containing formamide, acetamide, N‐methylformamide, and N‐methylacetamide. The individual hydrogen bonding energies in these heterogeneous chains are also in good agreement with those obtained from MP2 calculations with the BSSE correction, further demonstrating that our method is reasonable.     

Sarcoglycosides A – C,New O‐Glycosylglycerol Derivatives from the South China Sea Soft Coral Sarcophyton infundibuliforme

Chemical examination of the soft coral Sarcophyton infundibuliforme collected from the South China Sea resulted in the isolation of the three new O‐glycosylglycerol derivatives sarcoglycosides A–C ( 1 – 3 ), together with two known compounds, chimyl alcohol ( 4 ) and hexadecanol ( 5 ). Their structures were elucidated by combined spectral and chemical methods. All the compounds showed moderate toxicity to brine shrimps Artemia salina.     

Coherently Aligned Porphyrin‐Appended Polynorbornenes

You can append on me! Porphyrin‐appended polynorbornenes derived from 5,6‐endo‐fused N‐arylpyrrolidenonorbornenes have been shown to have coherently aligned pendant groups that exhibit exciton coupling and fluorescence quenching in the absorption and emission profiles (see figure).

     

Ultrafast Dynamics of o‐Bromofluorobenzene Studied by Time‐Resolved Photoelectron Imaging

Photodissociation dynamics and rotational wave packet coherences of o‐bromofluorobenzene are studied by femtosecond time‐resolved photoelectron imaging (see figure). The decay of different photoelectron rings shows the population decay of states from which the lifetimes of different states are determined. The variation of photoelectron angular distributions reflects the evolution of rotational coherences.

     

Cover Picture: Toroidal Micelles of Uniform Size from Diblock Copolymers (Angew. Chem. Int. Ed. 25/2009)

Pure toroidal micelles of highly uniform shape and size are presented by T. Chang et al. in their Communication on page 4594 ff. The donut‐shaped micelles are prepared by spontaneous self‐assembly of a polyisoprene‐block‐poly(2‐vinylpyridine) copolymer, and are stable enough to act as a template for the growth of gold nanoparticles along the ring surface.

     

Chemical Oxidative Degradation of Acridine Orange Dye in Aqueous Solution by Fenton's Reagent

Degradation of acridine orange (AO) in aqueous solution by Fenton's reagent (Fe²⁺ and H₂O₂) was investigated. The effects of different reaction parameters such as initial AO concentration, pH value of solution, ferrous concentration, hydrogen peroxide concentration, and the presence of chloride ion on the oxidative degradation of AO were investigated. Under optimum conditions, 2 mM H₂O₂, 0.4 mM Fe²⁺ and pH 3.0, the initial 0.2 mM AO solution was reduced by 95.8% within 10 min. The primary intermediates of the degradation reaction of AO were identified. The analytical results indicated that the N‐de‐methylation degradation of AO dye took place in a stepwise manner to yield mono‐, di‐, tri‐, and tetra‐N‐de‐methylated AO species generated during the Fenton process. The probable degradation pathways were proposed and discussed.     

Synthesis of Crosslinked Sulfonated Poly(phenylene sulfide sulfone nitrile) for Direct Methanol Fuel Cell Applications

With a view towards direct methanol fuel cell applications, novel sulfonated poly(phenylene sulfide sulfone nitrile) (sPPSSfN) has been prepared and subsequently crosslinked by a Friedel‐Craft reaction using 4,4′‐oxybis(benzoic acid) as a crosslinker to achieve lower water swelling and lower methanol permeability. The dimensional change of SPPSSfN40 is 43.7% in 90 °C liquid water but that of the crosslinked membrane, XsPPSSfN40, is 23.3% while maintaining proton conductivity at 0.22 S · cm⁻¹. These results show that the Friedel‐Craft crosslinking of the novel sPPSSfN membrane effectively reduces water uptake and the degree of swelling while improving the dimensional stability and maintaining high proton conductivity.

     

Discriminating Among Co‐monomer Sequence Distributions in Random Copolymers Using Interaction Chromatography

Interaction chromatography has been employed to validate that adsorption of poly[styrene‐co‐(4‐bromostyrene)] (PBr_xS) random copolymers, where x denotes the mole fraction of 4‐bromostyrene (4–BrS) in PBr_xS in solution depends on the average number of adsorptive segments, the type of adsorbing substrate, and on the co‐monomer sequence distribution in PBr_xS.