Crystallographic report: catena‐Aqua(2,2′‐bipyrimidine)lithium(I) perchlorate

A lithium(I) coordination polymer has been formed from LiClO₄ and the 2,2′‐bipyrimidine (bpym) ligand in which each square pyramidal lithium(I) atom is coordinated in the basal plane by four nitrogen donor atoms derived from two bpym ligands and one water molecule at the apical position. These are connected into a layer structure via hydrogen‐bonding interactions involving the perchlorate anions. Copyright © 2004 John Wiley & Sons, Ltd.     

Living/controlled radical copolymerization of N‐substituted maleimides with styrene in 1‐butyl‐3‐methylimidazolium hexafluorophosphate and anisole

The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < M_w/M_n < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF₆] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003     

Yellow‐light‐emitting cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative: Its synthesis and optical properties

A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λ_max ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003     

Concentrations of hazardous heavy metals in environmental samples collected in Xiamen, China, as determined by vapor generation non-dispersive atomic fluorescence spectrometry.

Non-dispersive atomic fluorescence spectrometry (NDAFS) coupled with vapor generation (VG) sample introduction was applied to the determination of the concentrations of hazardous heavy metals, such as arsenic, cadmium, lead and mercury, in seawater, soils and total airborne particulate matter (PM) collected around the Xiamen area in China. Almost 100% sample introduction efficiency was achieved by using thiourea and ascorbic acid for the pre-reduction of As(V) to As(III), K3Fe(CN)6 and tartaric acid for pre-oxidation of Pb(II) to Pb(IV), and masking the interferences arising from the co-existing transition metals to As, Cd, Hg and Pb during their vapor generation process. Moreover, a novel sample pretreatment device was developed to avoid the loss of mercury, lead, cadmium and arsenic during sample pretreatment. With such methods, the detection limit (DL) of arsenic, cadmium, lead and mercury was down to 0.08, 0.03, 0.05, 0.01 ng mL(-1) (3sigma), respectively. The relative standard deviations (RSD, n = 11) for arsenic, cadmium, lead and mercury at 10 ng mL(-1) were 0.9%, 1.6%, 1.3% and 2.0%, respectively. The concentrations of hazardous heavy metals in the environmental samples collected in Xiamen, China are in the range from 0.02 +/- 0.001 ng mL(-1) in seawater to 15.3 +/- 0.2 microg g(-1) in soils. Besides flame/GF-AAS and ICP-AES/MS, VG-NDAFS should be another choice for the determination of hazardous heavy metals in environmental samples.     

Effect of end groups on complexation kinetics between cyclodextrins and guest polymers

α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006     

Crystallographic report: Bis(norfloxacin)dilead(II) tetranitrate, [Pb2(H‐Norf)2(ONO2)4]

The centrosymmetric binuclear structure of [Pb₂(H‐Norf)₂(ONO₂)₄]shows the geometry around each lead(II) atom to be distorted trigonal bipyramidal with Pb–O distances ranging from 2.357(3) to 2.769(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Crystal structure and morphology of phenyl‐capped tetraaniline in the leucoemeraldine oxidation state

A series of crystals of phenyl‐capped tetraaniline in the leucoemeraldine oxidation state were obtained at different isothermal temperatures and were observed directly under transmission electron microscope. The crystals obtained at higher temperatures exhibit more perfect structures than those obtained at lower temperatures. Both the lamella thickness and the crystal size increase with crystallization temperature. The tetraaniline is apt to form larger scale crystals under lower degree of supercooling. However, their crystal structures keep steady with the crystallization temperature. The tetramer was found to adopt a monoclinic lattice with unit cell parameter of a = 13.93 Å, b = 8.82 Å, c = 23.20 Å, and β = 95.03°, as determined using electron diffraction tilting method combined with wide‐angle X‐ray diffraction experiment. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 764–769, 2006     

Adsorption, desorption and activities of acid phosphatase on various colloidal particles from an Ultisol

Adsorption, desorption and activity of acid phosphatase on various soil colloidal particles and pure clay minerals were studied. Higher adsorption amounts and low percentage of desorption of acid phosphatase were found on fine soil clays (<0.2 μm). Electrostatic force and ligand exchange are the major driving forces that are involved in the adsorption of enzymes on soil clays. More enzyme molecules were adsorbed on soil clays in the presence of organic components. However, enzymes on organic clays were more easily released. One-third of the enzyme on goethite was adsorbed via ligand exchange process. Some other interactions, such as van der Waals force, hydrophobic force and hydrogen bonding may be more important in the adsorption of enzyme on kaolinite and the enzyme in this system cannot be easily removed. Coarse clays (0.2–2 μm) and inorganic soil clays had higher affinities for enzyme molecules than fine clays and organic clays, respectively. The activity of enzyme bound on soil clays was inhibited and the thermal stability was increased in the presence of organic matter. Data obtained in this study are helpful for a better understanding of the interactions of enzymes with inorganic and organic constituents in soil and associated environments.