Models for the lower S states of photosystem II: a trinuclear mixed-valent MnII/MnIV/MnII complex

The trinuclear complex Mn(3)(pko)(4)(CH(3)O)(2)(SCN)(2).CH(3)OH, 1, where Hpko is 2,2'-dipyridylketonoxime, is a rare example of a complex simultaneously containing Mn(II) and Mn(IV). X-ray crystallography and XANES spectroscopy clearly distinguish the Mn(II)(2)Mn(IV) valence isomer from the more commonly observed Mn(III)(2)Mn(II) formulation. Fits to variable-temperature magnetic susceptibility data indicate that the Mn(II) and Mn(IV) are ferromagnetically coupled (J = +6.13 cm(-1)) and that 1 has an S = (13)/(2) ground state.     

A New Iterative Approach for the Synthesis of Oligo(phenyleneethynediyl) Derivatives and Its Application for the Preparation of Fullerene?Oligo(phenyleneethynediyl) Conjugates as Active Photovoltaic Materials

Disymmetrically substituted oligo(phenyleneethynediyl) (OPE) derivatives were prepared from 2,5‐bis(octyloxy)‐4‐[(triisopropylsilyl)ethynyl]benzaldehyde ( 5 ) by an iterative approach using the following reaction sequence: i) Corey–Fuchs dibromoolefination, ii) treatment with an excess of lithium diisopropylamide, and iii) a metal‐catalyzed cross‐coupling reaction of the resulting terminal alkyne with 2,5‐diiodo‐1,4‐bis(octyloxy)benzene ( 3 ) (Schemes 2 and 3). Reaction of the OPE dimer 8 and trimer 13 thus obtained with N‐methylglycine and C₆₀ in refluxing toluene gave the corresponding C₆₀? OPE conjugates 16 and 17 , respectively (Scheme 4). On the other hand, treatment of the protected terminal alkynes 8 and 13 with Bu₄N followed by reaction of the resulting 9 and 14 with 4‐iodo‐N,N‐dibutylaniline under Sonogashira conditions yielded 10 and 15 , respectively (Schemes 2 and 3). Subsequent treatment with N‐methylglycine and C₆₀ in refluxing toluene furnished the C₆₀? OPE derivatives 18 and 19 (Scheme 4). Compound 9 was also subjected to a Pd‐catalyzed cross‐coupling reaction with 3 to give the centrosymmetrical OPE pentamer 20 (Scheme 5). Subsequent reduction followed by reaction of the resulting diol 21 with acid 22 under esterification conditions led to bis‐malonate 23 . Oxidative coupling of terminal alkyne 14 with the Hay catalyst gave bis‐aldehyde 24 (Scheme 6). Treatment with diisobutylaluminium hydride followed by dicylcohexylcarbodiimide‐mediated esterification with acid 22 gave bis‐malonate 26 . Finally, treatment of bis‐malonates 23 and 26 with C₆₀, I₂, and 1,8‐diazabicylco[5.4.0]undec‐7‐ene (DBU) in toluene afforded the bis[cyclopropafullerenes] 27 and 28 , respectively (Scheme 7). The C₆₀ derivatives 16 – 19, 27 , and 28 were tested as active materials in photovoltaic devices. Each C₆₀? OPE conjugate was sandwiched between poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate)‐covered indium tin oxide and aluminium electrodes. Interestingly, the performances of the devices prepared from the N,N‐dialkylaniline‐terminated derivatives 18 and 19 are significantly improved when compared to those obtained with 16, 17, 27 , and 28 , thus showing that the efficiency of the devices can be significantly improved by increasing the donor ability of the OPE moiety.     

Chemical recycling of poly(methyl methacrylate) by pyrolysis. Potential use of the liquid fraction as a raw material for the reproduction of the polymer

Pyrolysis of poly(methyl methacrylate) (PMMA) was studied as an effective way to recycle this polymer and recover its monomer methyl methacrylate (MMA). Experiments were carried out in a laboratory fixed bed reactor using either a model polymer or a commercial product based on PMMA as feedstock. Gaseous and liquid products obtained from polymer degradation were analysed and it was found that the oil fraction constituted mainly of the MMA monomer. Thus, the possibility of directly using the liquid product for the reproduction of the polymer was further investigated. Polymerizations accomplished in a differential scanning calorimeter using azo-bis-isobutyronitrile as initiator and different reaction temperatures. Results obtained were compared to corresponding data from polymerization of neat monomer. It was found that the pyrolysis liquid fraction can be polymerized and produce a polymer similar to the original PMMA. However, even small amounts of other organic compounds (mainly methyl esters) included in this fraction act as non-ideal reaction retarders, altering the reaction rate curve and lowering the glass transition temperature and the average molecular weight of the polymer produced.     

Step-scan TMDSC and high rate DSC study of the multiple melting behavior of poly(1,3-propylene terephthalate)

The multiple melting behavior of poly(1,3-propylene terephthalate) (PPT) samples after isothermal crystallization from the melt was studied. The step-scan temperature-modulated differential scanning calorimetry (TMDSC) and high rate DSC were used to investigate this behavior in conjunction with standard DSC, wide-angle X-ray diffraction (WAXD) and polarizing light microscopy (PLM). The effect of PPT average molecular weight on the melting was also examined. In general multiple endotherms after isothermal crystallization of PPT were attributed to a continuous crystal perfection process during the subsequent heating scan via melting-recrystallization-remelting. Multiple melting behavior was more pronounced for the low molecular weight PPT. Step-scan TMDSC showed that extensive recrystallization occurs in PPT samples, especially after rapid isothermal crystallization. In fact two recrystallization exothermic peaks were observed. High rate DSC revealed the initial morphology generated during the isothermal step and showed that the low and middle peaks are associated with melting of primary crystals while the high temperature peak should be attributed to melting of recrystallized material.     

On the mechanism of the laccase-mediator system in the oxidation of lignin

In an effort to elucidate the role of phenolic and non-phenolic lignin subunits in a laccase mediator (LM) system, vanillyl alcohol was oxidized with laccase in the presence and absence of the mediator 1-hydroxybenzotriazol (HBT). Furthermore, the role of phenolic, aliphatic hydroxyl, and carboxylic acid moieties in lignin degradation was elucidated by selectively blocking them. The modified samples were then subjected to laccase and laccase-HBT treatments. On the basis of this data it was possible to establish the role of this mediator. HBT mediates the oxidation of lignin by inducing side-chain oxidation and oxygen-addition products rather than oxidative coupling reactions.     

Tosylation and acylation of cellulose in 1-allyl-3-methylimidazolium chloride

Tosylation and acylation of cellulose were performed under mild reaction conditions using imidazolium based ionic liquids (ILs) as solvents. The non-degradative nature, lower viscosity, as well as higher solubility of cellulose in [amim]Cl encouraged us to carry out the reactions in this media. The reactions described here were optimised for this particular solvent in order to obtain different cellulose derivatives with high yields, homogeneity and degree of substitution (DS). Two reagents employed for the in situ activation of carboxylic acids were N,N′-carbonyldiimidazole (CDI) and 1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide hydrochloride (EDCI). Final products were characterised by solution and solid-state NMR techniques. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Approximating integrals of multivariate exponentials: A moment approach

We propose a method to calculate lower and upper bounds of some exponential multivariate integrals using moment relaxations and show that they asymptotically converge to the value of the integrals when the moment degree increases. We report computational results for integrals involving the normal distribution and exponential order statistic probabilities.     

Rheological transitions in asymmetric colloidal star mixtures

We examine the rheological transition from an arrested to a fluid state for different mixtures of star polymers with varying functionality and size ratios. As a general trend, we find that addition of smaller star polymers in an arrested, concentrated solution of larger ones brings about melting of the large star glass. At the same time, the dependence of the amount of additives needed to melt the glass has a nontrivial dependence on the size ratio. Theoretical analysis, based on effective interactions and Mode Coupling Theory, reproduces the experimental results and helps identify two distinct types of glasses in the composite system. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Negative refraction of low‐frequency electromagnetic waves

Features of anomalous refraction of low‐frequency electromagnetic waves are investigated in all‐semiconductor nonmagnetic superlattices with a periodic array of two‐dimensional electron gas layers under quantum Hall effect conditions. We show that the structure exhibits negative refraction on the lateral surface for all angles of incidence, in the frequency region which has no limitation from the low‐frequency side, and that for such intriguing properties it requires no resonance frequency and no negative component of the permittivity tensor. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)