Conductivity,structure, and thermal properties of chitosan‐based polymer electrolytes with nanofillers

This paper focus on the effect of nanosize (<50 nm BET) inorganic alumina (Al₂O₃) filler on the structural, conductivity, and thermal properties of chitosan‐based polymer electrolytes. Films of chitosan and its complexes were prepared using solution‐casting technique. Different amounts of Al₂O₃ viz., 3, 4.5, 6, 7.5, 9, 12, and 15 wt% were added to the highest room temperature conducting sample in the chitosan–salt system, i.e. sample containing 60 wt% chitosan–40 wt% NH₄SCN. The conductivity value of the sample is 1.29 × 10^?4 S cm^?1. On addition of 6 wt% Al₂O₃ filler the ionic conductivity increased to 5.86 × 10^?4 S cm^?1. The amide and amino peaks in the spectrum of chitosan at 1636 and 1551 cm^?1, respectively, shift to lower wavenumbers on addition of salt. The glass transition temperature T_g for the highest conducting composite is 190°C. The increase in T_g with increase in more than 6 wt% filler content is attributed to the increase in degree of crystallinity as proven from X‐ray diffraction studies. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of molecular weight and degree of deacetylation of chitosan on the formation of oil-in-water emulsions stabilized by surfactant-chitosan membranes

The objective of this study was to establish the influence of polyelectrolyte characteristics (molecular weight and charge density) on the properties of oil-in-water emulsions containing oil droplets surrounded by surfactant-polyelectrolyte layers. A surfactant-stabilized emulsion containing small droplets (d32 approximately 0.3 microm) was prepared by homogenizing 20 wt% corn oil with 80 wt% emulsifier solution (20 mM SDS or 2.5 wt% Tween 20, 100 mM acetate buffer, pH 3) using a high-pressure valve homogenizer. This primary emulsion was then diluted with various chitosan solutions to produce secondary emulsions with a range of chitosan concentrations (3 wt% corn oil, 0-1 wt% chitosan). The influence of the molecular characteristics of chitosan on the properties of these emulsions was examined by using chitosan ingredients with different molecular weights (MW approximately 15, 145, and 200 kDa) and degree of deacetylation (DDA approximately 40, 77, and 92%). The electrical charge and particle size of the secondary emulsions were then measured. Extensive droplet aggregation occurred when the chitosan concentration was below the amount required to saturate the droplet surfaces, but stable emulsions could be formed at higher chitosan concentrations. The zeta-potential and mean diameter (d32) of the particles in the secondary emulsions was not strongly influenced by chitosan MW, however the chitosan with the lowest DDA (40%) produced droplets with smaller mean diameters and zeta-potentials than the other two DDA samples examined. Interestingly, we found that stable multilayer emulsions could be formed by mixing medium or high MW chitosan with an emulsion stabilized by a non-ionic surfactant (Tween 20) due to the fact the initial droplets had some negative charge. The information obtained from this study is useful for preparing emulsions stabilized by multilayer interfacial layers.     

Synthesis of polymer microspheres functionalized with chiral ligand by precipitation polymerization and their application to asymmetric transfer hydrogenation

Monodisperse, crosslinked poly(divinylbenzene) and poly(methacrylic acid‐co‐ethylene glycol dimethacrylate) microspheres with (1R,2R)‐N¹‐toluenesulfonyl‐1,2‐diphenylethylene‐1,2‐diamine ((R,R)‐TsDPEN) moiety were successfully prepared by precipitation polymerization. Introduction site of the (R,R)‐TsDPEN moiety into the polymer microspheres could be controlled by changing the order of addition of the corresponding monomers. The functionalized polymer microspheres were applied to asymmetric transfer hydrogenation of ketone and imine. Polymer microsphere‐supported chiral catalysts showed good reactivity and enantioselectivity in the catalytic asymmetric transfer hydrogenations. Chiral secondary alcohol was quantitatively obtained with 94% ee in the asymmetric transfer hydrogenation of acetophenone in water. We also found that introduction site of the chiral catalyst and hydrophobicity of the microspheres, as well as degree of the crosslinking, affected the yield and enantioselectivity of chiral product in this reaction. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3340–3349, 2010     

Asymmetric Catalysis by Vitamin B12. The Mechanism of the Cob(I)alamin-Catalyzed Isomerization of 1,2-Epoxycyclopentane to (R)-Cyclopent-2-enol

The isomerization of 1,2-epcxycyclopentane ( 1 ) to enantiomerically enriched (R)-cyclopent-2-enol ( 2 ) in protic solvents is catalyzed by cob(I)alamin. The enantiomeric excess (e.e.) of (R)- 2 is usually ca. 60%; it is only slightly dependent on the temperature, but increases with decreasing dielectric constant ε of the solvent. Standard kinetic methods show the reaction to be first order in vitamin B₁₂ and zero order in 1 . The rate constant increases exponentially with increasing ε of the solvent. An Arrhenius plot at ε = 40 gives activation parameters ΔH^≠ = 78 ± 4 kJ·mol^?1 and ΔS^≠ = ?49 ± 1 J·mol^?1·K^?1. The isomerization 1 → 2 proceeds in two steps (Schemes 2 and 7): (i) The epoxide ring is first opened by the proton-assisted fast and irreversible nucleophilic attack of the chiral Co^I catalyst to form diastereoisomeric (1R,2R)- and (1S,2S)-(2-hydroxycyclo-pentyl)cob(III)alamins 6 in a ratio of ca. 4:1 which are the dominant species in the steady state; (ii) The intermediates 6 then decompose in the rate-limiting step to form 2 and recycled catalyst. Experiments with specifically ²H-labeled 1 showed the hydro-cobalt elimination 6 → 2 to be non-stereoselective. It proceeds via reversible Co? C bond homolysis to a free 2-hydroxycyclopentyl radical from which stereoelectronically controlled H-abstraction by Co¹¹ takes place.     

The influence of CaCO3 filler component on thermal decomposition process of PP/LDPE/DAP ternary blend

Polypropylene‐low density polyethylene (PP‐LDPE) blends involving PP‐LDPE (90/10 wt%.) with (0.06 wt%) dialkyl peroxide (DAP) and different amounts (5, 10, 20 wt%) of calcium carbonate (CaCO₃) were prepared by melt‐blending with a single‐screw extruder. The effect of addition of CaCO₃ on thermal decomposition process and kinetic parameters, such as activation energy and pre‐exponential factor of PP‐LDPE blend with DAP matrix, was studied. The kinetics of the thermal degradation of composites was investigated by thermogravimetric analysis in dynamic nitrogen atmosphere at different heating rates. TG curves showed that the thermal decomposition of composites occurred in one weight‐loss stage. The apparent activation energies of thermal decomposition for composites, as determined by the Tang method (TM), the Kissinger–Akahira–Sunose method (KAS), the Flynn–Wall–Ozawa method (FWO), and the Coats–Redfern (CR) method were 156.6, 156.0, 159.8, and 167.7 kJ.mol^?1 for the thermal decomposition of composite with 5 wt% CaCO₃, 191.5, 190.8, 193.1, and 196.8 kJ.mol^?1 for the thermal decomposition of composite with 10 wt% CaCO₃, and 206.3, 206.1, 207.5, and 203.8 kJ mol^?1 for the thermal decomposition of composite with 20 wt% CaCO₃, respectively. The most likely decomposition process for weight‐loss stages of composites with CaCO₃ content 5 and 10 wt% was an A_n sigmoidal type. However, the most likely decomposition process for composite with CaCO₃ content 20 wt% was an R_n contracted geometry shape type in terms of the CR and master plots results. It was also found that the thermal stability, activation energy, and thermal decomposition process were changed with the increase in the CaCO₃ filler weight in composite structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Vitamin A and vitamin E interaction behavior on chitosan microspheres

Chitosan is a biodegradable natural polymer with great potential for pharmaceutical applications due to its biocompatibility, high charge density, and non-toxicity. In this study, chitosan microspheres were successfully prepared by an adapted method of coagulation/dispersion. The degree of deacetylation of chitosan powder was obtained by NMR ¹H and FTIR techniques. Chitosan powder and chitosan microspheres were characterized by BET surface area and scanning electron microscopy (SEM). The interactions among the chitosan microspheres and the vitamins A and E were characterized by FTIR. In order to evaluate the ability of interaction of vitamin A and vitamin E with the chitosan microspheres, the thermodynamic parameters were followed by calorimetric titration. Different experimental approaches were applied, such as adsorption isotherms, kinetics and thermodynamics studies. The obtained results showed that the interactions of chitosan microspheres with the vitamins were spontaneous, enthalpically and entropically favorable, indicating that the chitosan microspheres can be used with success in the controlled release of these vitamins.     

Molecular Recognition of Pyranosides by a Family of Trimeric, 1,1′-Binaphthalene-Derived Cyclophane Receptors

The synthesis and carbohydrate-recognition properties of a new family of optically active cyclophane receptors, 1 – 3 , in which three 1,1′-binaphthalene-2,2′-diol spacers are interconnected by three buta-1,3-diynediyl linkers, are described. The macrocycles all contain highly preorganized cavities lined with six convergent OH groups for H-bonding and complementary in size and shape to monosaccharides. Compounds 1 – 3 differ by the functionality attached to the major groove of the 1,1′-binaphthalene-2,2′-diol spacers. The major grooves of the spacers in 2 are unsubstituted, whereas those in 1 bear benzyloxy (BnO) groups in the 7,7′-positions and those in 3 2-phenylethyl groups in the 6,6′-positions. The preparation of the more planar, D₃-symmetrical receptors (R,R,R)- 1 (Schemes 1 and 2), (S,S,S)- 1 (Scheme 4), (S,S,S)- 2 (Scheme 5), and (S,S,S)- 3 (Scheme 8) involved as key step the Glaser-Hay cyclotrimerization of the corresponding OH-protected 3,3′-diethynyl-1,1′-binaphthalene-2,2′-diol precursors, which yielded tetrameric and pentameric macrocycles in addition to the desired trimeric compounds. The synthesis of the less planar, C₂-symmetrical receptors (R,R,S)- 2 (Scheme 6) and (S,S,R)- 3 (Scheme 9) proceeded via two Glaser-Hay coupling steps. First, two monomeric precursors of identical configuration were oxidatively coupled to give a dimeric intermediate which was then subjected to macrocyclization with a third monomeric 1,1′-binaphthalene precursor of opposite configuration. The 3,3′-dialkynylation of the OH-protected 1,1′-binaphthalene-2,2′-diol precursors for the macrocyclizations was either performed by Stille (Scheme 1) or by Sonogashira (Schemes 4, 5, and 8) cross-coupling reactions. The flat D₃-symmetrical receptors (R,R,R)- 1 and (S,S,S)- 1 formed 1 : 1 cavity inclusion complexes with octyl 1-O-pyranosides in CDCl₃ (300 K) with moderate stability (ΔG⁰ ca. −3 kcal mol⁻¹) as well as moderate diastereo- (Δ(ΔG⁰) up to 0.7 kcal mol⁻¹) and enantioselectivity (Δ(ΔG⁰)=0.4 kcal mol⁻¹) (Table 1). Stoichiometric 1 : 1 complexation by (S,S,S)- 2 and (S,S,S)- 3 could not be investigated by ¹H-NMR binding titrations, due to very strong signal broadening. This broadening of the ¹H-NMR resonances is presumably indicative of higher-order associations, in which the planar macrocycles sandwich the carbohydrate guests. The less planar C₂-symmetrical receptor (S,S,R)- 3 formed stable 1 : 1 complexes with binding free enthalpies of up to ΔG⁰=−5.0 kcal mol⁻¹ (Table 2). With diastereoselectivities up to Δ(ΔG⁰)=1.3 kcal mol⁻¹ and enantioselectivities of Δ(ΔG⁰)=0.9 kcal mol⁻¹, (S,S,R)- 3 is among the most selective artificial carbohydrate receptors known.     

Non-isothermal Kinetics of the First-stage Decomposition Reaction of the Complex of Terbium p-Methylbenzoate with 1,10-Phenanthroline

The thermal behavior of Tb₂ (p‐MBA)₆(phen)₂ (p‐MBA=p‐methylbenzoate; phen=1,10‐phenanthroline) in a static air atmosphere was investigated by TG‐DTG, SEM and IR techniques. The thermal decomposition of the Tb₂(p‐MBA)₆(phen)₂ occurred in three consecutive stages at T_P of 354, 457 and 595 °C. By Malek method, RO (n<1) was defined as kinetic model for the first‐step thermal decomposition. The activation energy (E) of this step is 170.21 kJ·mol^‐1, the enthalpy of activation (ΔH^≠) 164.98 kJ·mol^‐1, the Gibbs free energy of activation (ΔG^≠) 145.04 kJ·mol^‐1, the entropy of activation (ΔS^≠) 31.77 J·mol^‐1·K^‐1, and the pre‐exponential factor (A) 10^15.21 s^‐1.     

Conductivity of crosslinked poly(N-vinylpyrrolidone) gel film containing surfactant as electrolyte salt

New polymeric solid electrolyte films, consisting of crosslinked poly(N-vinylpyrrolidone) (PVPD) as matrix, and surfactant, sodium deoxycholate (NaDC), lithium deoxycholate (LiDC), sodium laulylsulfate (R₁₂OSO₃Na), or sodium palmitate (R₁₅COONa) as electrolyte salt, are prepared; their basic structure and conductivity dependence on temperature are reported. The structure of the electrolytes is amorphous. Their conductivity is 3.1 × 10^?5 S cm^?1 (containing NaDC), 8.42 × 10^?6 S cm^?1 (LiDC), 2.18 × 10^?4 S cm^?1 (R₁₂OSO₃Na), and 7.27 × 10^?5 S cm^?1 (R₁₅COONa) at 20°C. Their temperature dependence of the conductivity is similar to that of liquid electrolyte rather than that of usual polymeric solid electrolyte, i.e., the WLF-type dependence. The values of activation energy of conductivity (E_a) were PVPD, 25.5 kJ mol^?1; PVPD/NaDC, 21.4 kJ mol^?1; PVPD/LiDC, 25.3 kJ mol^?1; PVPD/R₁₂OSO₃Na, 17.2 kJ mol^?1; PVPD/R₁₅COONa, 18.7 kJ mol^?1. © 1993 John Wiley & Sons, Inc.     

Kinetics of the thermal decomposition of [Co(NH3)6]2(C2O4)3·4H2O

The thermal decomposition of [Co(NH₃)₆]₂(C₂O₄)₃·4H₂O was studied under isothermal conditions in flowing air and argon. Dissociation of the above complex occurs in three stages. The kinetics of the particular stages thermal decomposition have been evaluated. The R_N and/or A_M models were selected as those best fitting the experimental TG curves. The activation energies,E, and lnA were calculated with a conventional procedure and by a new method suggested by Kogaet al. [10, 11]. Comparison of the results have showed that the Arrhenius parameters values estimated by the use of both methods are very close. The calculated activation energies were in air: 96 kJ mol^–1 (R_1.575, stage I); 101 kJ mol^–1 (Ain1.725 stage II); 185 kJ mol^–1 (A _2.9, stage III) and in argon: 66 kJ mol^–1 (A _1.25, stage I); 87 kJ mol^–1 (A _1.825, stage II); 133 kJ mol^–1 (A _2.525, stage III).     

LOW MOLECULAR WEIGHT O-CARBOXYMETHYLATED CHITOSANS DERIVED FROM IRRADIATED CHITOSAN AND THEIR ANTIBACTERIAL ACTIVITY*

 Original chitosan with M_v of 2.7 × 10⁵ was degraded by irradiation with γ-rays and a series of low molecular weight O-carboxymethylated chitosans (O-CMCh) were prepared based on the irradiated chitosan. A kinetic model of the irradiation of chitosan was put forward. Results show that the irradiation degradation of chitosan obeys the rule of random degradation and the degree of deacetylation of irradiated chitosan is slightly raised. The antibacterial activity of O-CMCh is significantly influenced by its MW, and a suppositional antibacterial peak appears when M_v is equal to 2 × 10⁵.     

Molecular Clefts Derived from 9,9′-spirobi[9H-fluorene] for enantioselective complexation of pyranosides and dicarboxylic acids

The molecular clefts (R)- and (S)- 3 , incorporating 9,9′-spirobi[9H-fluorene] as a spacer and two N-(5,7-dimethyl-1,8-naphthyridin-2-yl)carboxamide (CONH(naphthy)) units as H-bonding sites were prepared via the bis(succinimid-N-yl esters) of (R)-and (S)-9,9′-spirobi[9H-fluorene]-2,2′-dicarboxylic acid ( 5 ). Derivative 6 , with one CONH(naphthy) unit and one succinimid-N-yl ester residue allowed easy access to spirobifluorene clefts with two different H-bonding sites, as exemplified by the synthesis of 4 . Binding studies with (R)- and (S)- 3 and optically active dicarboxylic acids in CDCl₃ exhibited differences in free energy of the formed diastereoisomeric complexes (Δ(ΔGº)) between 0.5 and 1.6 kcal mol^?1 (T 300 K). Similar enantioselectivities were observed with the spirobifluorene clefts (R)- and (S)- 1 , bearing two N-(6-methylpyridin-2-yl)carboxamide (CONH(py)) H-bonding sites. The thermodynamic quantities ΔHº and ΔSº for the recognition processes with (R)- and (S)- 1 were determined by variable-temperature ¹H-NMR titrations and compared to those with (R)- and (S)- 2 , which have two CONH(py) moieties attached to the 6,6′-positions of a conformationally more flexible 1,1′-binaphthyl cleft. All association processes showed high enthalpic driving forces which are partially compensated by unfavorable changes in entropy. Pyranosides bind to the optically active clefts 1 and 3 in CDCl₃ with ?ΔGº = 3.0–4.3 kcal mol^?1. Diastereoisomeric selectivities up to 1.2 kcal mol^?1 and enantioselectivities up to 0.4 kcal mol^?1 were observed. Cleft 4 and N-(5,7-dimethyl-1,8-naphthyridin-2-yl)acetamide ( 25 ) complexed pyranosides 22–24 as effectively as 3 indicating that only one CONH(naphthy) site in 3 associates strongly with the sugar derivatives. Based on the X-ray crystal structure of 3 , a computer model for the complex between (S)- 3 and pyranoside 22 was constructed. Molecular-dynamics (MD) simulations showed that differential geometrical constraints are at the origin of the high enantioselectivity in the complexation of dicarboxylic acid (S)- 7 by (R)- and (S)- 1 and (R)- and (S)- 3 .     

Effect of CaCO3 Filler Component on Solid State Decomposition Kinetic of PP/LDPE/CaCO3 Composites

In this study, the effect of addition Calcium carbonate (CaCO₃) filler component on solid state thermal decomposition procedures of Polypropylene-Low Density Polyethylene (PP-LDPE; 90/10 wt%) blends involving different amounts (5, 10, 20 wt%) Calcium carbonate (CaCO₃) was investigated using thermogravimetry in dynamic nitrogen atmosphere at different heating rates. An integral composite procedure involving the integral iso-conversional methods such as the Tang (TM), the Kissinger-Akahira-Sunose method (KAS), the Flynn-Wall-Ozawa (FWO), an integral method such as Coats-Redfern (CR) and master plots method were employed to determine the kinetic model and kinetic parameters of the decomposition processes under non-isothermal conditions. The Iso-conversional methods indicated that the thermal decomposition reaction should conform to single reaction model. The results of the integral composite procedures of TG data at various heating rates suggested that thermal processes of PP-LDPE-CaCO₃ composites involving different amounts of CaCO₃ filler component (5, 10, 20 wt%) followed a single step with approximate activation energies of 226.7, 248.9, and 252.0 kJ.mol^{? 1} according to the FWO method, respectively and those of 231.3, 240.1 and 243.0 kJ mol^{? 1} at 5°C min^{? 1} according to the Coats-Redfern method, the reaction mechanisms of all the composites was described from the master plots methods and are P_n model for composite C-1, R_n model for composites C-2 and C-3, respectively. It was found that the thermal stability, activation energy and thermal decomposition process changed by the increasing CaCO₃ filler weight in composite structure.     

Data on the thermochemistry of azoalkanes

The rate constant of the primary decomposition step was determined for four symmetrical and four unsymmetrical azoalkanes. From the experimental activation energies and some literature enthalpy data, the following enthalpies of formation of radicals and group contributions were calculated: ΔH_? (CH₃N₂) = 51.5 ± 1.8 kcal mol^?1, ΔH_? (C₂H₅N₂) = 44.8 ± 2.5 kcal mol^?1, ΔH_? (2?C₃H₇N₂) = 37.9 ± 2.2 kcal mol^?1, [N_A-(C)] = 27.6 ± 3.7 kcal mol^?1, [N_A-(?_A) (C)] = 61.2 ± 3.1 kcal mol^?1.     

Diagnostic cyclisation reactions which follow phosphate transfer to carboxylate anion centres for energised [M-H]- anions of pTyr-containing peptides

The low‐energy negative ion phosphoTyr to C‐terminal ‐CO₂PO₃H₂ rearrangement occurs for energised peptide [M–H]^– anions even when there are seven amino acid residues between the pTyr and C‐terminal amino acid residues. The rearranged C‐terminal ‐CO₂PO₂H(O^–) group effects characteristic S_Ni cyclisation/cleavage reactions. The most pronounced of these involves the electrophilic central backbone carbon of the penultimate amino acid residue. This reaction is aided by the intermediacy of an H‐bonded intermediate in which the nucleophilic and electrophilic reaction centres are held in proximity in order for the S_Ni cyclisation/cleavage to proceed. The ΔG_reaction is +184 kJ mol^?1 with the barrier to the S_Ni transition state being +240 kJ mol^?1 at the HF/6‐31 + G(d)//AM1 level of theory. A similar phosphate rearrangement from pTyr to side chain CO₂^– (of Asp or Glu) may also occur for energised peptide [M–H]^– anions. The reaction is favourable: ΔG_reaction is ?44 kJ mol^?1 with a maximum barrier of +21 kJ mol^?1 (to the initial transition state) when Asp and Tyr are adjacent. The rearranged species R¹‐Tyr‐NHCH(CH₂CO₂PO₃H^–)COR² (R¹ = CHO; R² = OCH₃) may undergo an S_Ni six‐centred cyclisation/cleavage reaction to form the product anion R¹‐Tyr(NH^–). This process has a high energy requirement [ΔG_reaction = +224 kJ mol^?1, with the barrier to the S_Ni transition state being +299 kJ mol^?1]. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation of Thermosensitive Hollow Imprinted Microspheres via Combining Distillation Precipitation Polymerization and Thiol‐ene Click Chemistry

Hollow molecular imprinted polymer microspheres were prepared by distillation precipitation polymerization with (S)‐(+)‐ibuprofen (S‐IBF) as template molecule and acrylamide (AM) as functional monomer. Using the silicon dioxide (SiO₂, 180 nm) modified by 3‐(trimethoxysilyl)propyl methacrylate (MPS) as the template microspheres, the molecular imprinted shells were coated on successfully (SiO₂@MIPs). The thermosensitive SiO₂@MIPs‐PNIPAM core‐shell microspheres were subsequently prepared by grafting the PNIPAM chains (M_n=1.21×10⁴ g/mol, polydispersity index=1.30), which were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization, on the surface of SiO₂@MIPs microspheres via the thiol‐ene click chemistry. The grafting density of PNIPAM brushes on the SiO₂@MIPs microspheres was about 0.18 chains/nm². After HF etching, the hollow imprinted microspheres were finally obtained. For thermosensitivity analysis, the phase transition temperatures of multifunctional nanoparticles were measured by DSL at 25°C and 45°C respectively, and the sizes of the microspheres changed by about 35 nm. The modified microspheres presented excellent controlled release property to S‐IBF, moreover about half amount of the adsorptions passed into acetonitrile‐water solution through the specific holes of imprinted shell at 25°C under vibration.     

Formation and Dissociation of Tetrahedral Nickel(II) and Cobalt(II) Complexes of ‘Dithioimidodiphosphato’ Ligands,Measurement of Kinetically Determined Stability Constants,and Kinetic Investigations of the Rapid Formation of Tetrahedral Bis(ligand)copper(II) Complexes and Their Rates of Reduction to Trinuclear Copper(I) Species

The stopped‐flow technique was used to measure the rates of formation and dissociation of tetrahedral [ML₂] complexes (M²⁺=Ni²⁺ or Co²⁺) of four bidentate S₂‐donor ‘dithioimidodiphosphato’ ligands L^? (HL=[R¹R²P(?S)]NH[P(?S)R³R⁴], R¹ to R⁴=alkyl) at 25.0° in MeOH/H₂O 95 : 5 (v/v) solution and in the presence of either MOPS (=3‐(morpholin‐4‐yl)propane‐1‐sulfonic acid) or 2,6‐lutidine (=2,6‐dimethylpyridine) buffers. The kinetically determined equilibrium formation constants for [ML]⁺ ions (M=Ni or Co) are 10^?5 K=0.50±0.01 or 1.64±0.07 l mol^?1 for L=L³ (R¹=R²=Me(CH₂)₂CH(Me), R³=R⁴=Me₂CH), 1.27±0.02 or 7.93±0.09 l mol^?1 for L=L⁷ (R¹ to R⁴=Me₂CHCH₂), 0.88±0.04 or 3.84±0.13 l mol^?1 for L=L⁸ (R¹ to R⁴=Me₂CH), and in case of Ni²⁺ 1.88±0.04 l mol^?1 for L=L⁶ (R¹=R³=Bu, R²=R⁴=^tBu) (see Table 3; for L³ and L⁶–L⁸, see Table 1). Whereas the tetrahedral Ni²⁺ complexes dissociate more slowly than the analogous Co²⁺ species, in all cases, the Co²⁺ complexes are more stable than those of Ni²⁺ due to their larger formation rate constants (Table 3). Reactions of Cu²⁺ with eight ligands HL (R¹ to R⁴=alkyl, alkoxy, aryl, and aryloxy) show that formation of intensely colored tetrahedral [Cu^IIL₂] species is too fast be measured with the available stopped‐flow apparatus (t_1/2<2 ms), but the subsequent rates of reduction of [Cu^IIL₂] to give trinuclear products [Cu^I₃L₃] are measurable. An X‐ray analysis establishes the structure of one of the [Cu₃L₃] complexes, where R¹=R²=Me₂CHO and R³=R⁴=2‐(tert‐butyl)phenyl (L=L⁵), and a multiwavelength stopped‐flow kinetic experiment establishes the spectrum of a tetrahedral [Cu^IIL₂] species prior to the reduction reactions. The redox reactions proceed at 25.0° with first‐order rate constants in the range 0.285 s^?1 (R¹ to R⁴=PhO; L=L¹¹) to 2.58?10^?4 s^?1 (R¹ to R⁴=Me₂CHCH₂; L=L⁷) (Table 4).     

Mechanism and selectivity of the dinuclear iron benzoyl-coenzyme A epoxidase BoxB

Benzoyl-CoA epoxidase is a dinuclear iron enzyme that catalyzes the epoxidation reaction of the aromatic ring of benzoyl-CoA with chemo-, regio- and stereo-selectivity. It has been suggested that this enzyme may also catalyze the deoxygenation reaction of epoxide, suggesting a unique bifunctionality among the diiron enzymes. We report a density functional theory study of this enzyme aimed at elucidating its mechanism and the various selectivities. The epoxidation is suggested to start with the binding of the O₂ molecule to the diferrous center to generate a diferric peroxide complex, followed by concerted O–O bond cleavage and epoxide formation. Two different pathways have been located, leading to (2S,3R)-epoxy and (2R,3S)-epoxy products, with barriers of 17.6 and 20.4 kcal mol^–1, respectively. The barrier difference is 2.8 kcal mol^–1, corresponding to a diastereomeric excess of about 99 : 1. Further isomerization from epoxide to phenol is found to have quite a high barrier, which cannot compete with the product release step. After product release into solution, fast epoxide–oxepin isomerization and racemization can take place easily, leading to a racemic mixture of (2S,3R) and (2R,3S) products. The deoxygenation of epoxide to regenerate benzoyl-CoA by a diferrous form of the enzyme proceeds via a stepwise mechanism. The C2–O bond cleavage happens first, coupled with one electron transfer from one iron center to the substrate, to form a radical intermediate, which is followed by the second C3–O bond cleavage. The first step is rate-limiting with a barrier of only 10.8 kcal mol^–1. Further experimental studies are encouraged to verify our results.     

Chiral 1,1′-Binaphthyl Molecular Clefts for the Complexation of Excitatory Amino-Acid Derivatives

The complexation of N-benzyloxycarbonyl (Cbz) derivatives of the excitatory amino acids L -aspartic acid (Asp; 1 ), L -glutamic acid (Glu; 3 ), and, for the first time, L -kainic acid ((2S,3S,3S)-2-carboxy-4-(1-methylethenyl)pyrrolidine-3-acetic acid; Kai; 5 ) was studied in CDCl₃ with a diversity of chiral receptors consisting of a 1,1′-binaphthyl spacer with (carboxamido)pyridine (CONH(py)) functionality attached to the 6,6′-positions in the major groove. Receptors of type A possess two N-(pyridin-2-yl)carboxamide H-bonding sites (e.g. 7 ), whereas type B-receptors have two N-(pyridine-6,2-diyl)acetamide residues attached (e.g. 8 and 9 ). Complexes of excitatory amino-acid derivatives and other, achiral α,β-dicarboxylic acids with these receptors are primarily stabilized by two sets of C?O···H? N and O? H ··· N H-bonds. Optically active type-A receptors such as (R)- and (S)- 7 showed a preference for the larger Glu derivative, whereas type- B receptors such as (R)- and (S)- 8 and (R)- and (S)- 9 formed more stable complexes with the smaller Cbz-Asp. To improve the poor enantioselectivity shown by 7–9 , additional functionality was introduced at the 7,7′-positions of the 1,1′-binaphthyl spacer, and the nature of the H-bonding sites in the 6,6′-positions was varied. Screening the diversity of new racemic receptors for binding affinity, which had been shown in many examples by Cram to correlate with enantioselectivity, demonstrated that (+)- 10 and (+)- 11 formed the most stable complexes with dicarboxylic acids, and these receptors were synthesized in enantiomerically pure form. Both are type- B binders and contain additional PhCH₂O ( 10 ) and MeO ( 11 ) groups in the 7,7′-positions. By ¹H-NMR binding titrations, the complexation of (R)- and (S)- 10 and (R)- and (S)- 11 with the excitatory amino-acid derivatives was studied in CDCl₃, and association constants K_a between 10³ and 2 · 10⁵ l mol^?1 were measured for the 1:1 host-guest complexes formed. Whereas both 10 and 11 formed stable complexes, enantioselective binding was limited to the PhCH₂O-substituted receptor 10 , with the (R)-enantiomer complexing Cbz-Asp by 0.7 kcal mol^?1 more tightly than the (S)-enantiomer. The structures of the diastereoisomeric complexes were analyzed in detail by experimental methods (complexation-induced changes in ¹H-NMR chemical shifts, ¹H{¹H} nuclear Overhauser effect (NOE) difference spectroscopy) and computer modeling. These studies established that an unusual variety of interesting aromatic interactions and secondary electrostatic interactions are responsible for both the high binding affinity (? ΔG° up to 7.2 kcal mol^?1) and the enantioselection observed with (R)- and (S)- 10 . In an approach to enhance the enantioselectivity by reducing the conformational flexibility of the 1,1′-binaphthyl spacer, an additional crown-ether binding site was attached to the 2,2′-positions in the minor groove of the type- B receptors (R)- and (S)- 48 . Both the binding affinity and the enantioselectivity (Δ(ΔG°) up to 0.7 kcal mol^?1) in the complexation of the excitatory amino-acid derivatives by (R)- and (S)- 48 were not altered upon complexation of Hg(CN)₂ at the crown-ether binding site, demonstrating lack of cooperativity between the minor- and major-groove recognition sites.