Exploring the relationship between cocrystal stability and symmetry: is Wallach's rule applicable to multi-component solids?

Comparison of structure and hydration stability of pairs of chiral and racemic binary cocrystals indicates that the racemic solid is more stable than the chiral one; we illustrate that this difference might arise from intermolecular (crystal packing) factors in one case, while intramolecular (molecular conformation) factors are more significant in the other.     

Synergy between Brønsted acid sites and Lewis acid sites

Synergy between Br?nsted acid sites and Lewis acid sites in mesoporous Al-Zr-TUD-1 was demonstrated to exist in Br?nsted acid catalysed reactions, but not in Lewis acid catalysed reactions.     

Iodide-catalysed self-assembly of donor-acceptor [3]catenanes

Charged donor-acceptor [3]catenanes comprising the pi-accepting cyclobis(paraquat-4,4'-biphenylene) and pi-donating aromatic crown ether macrocycles have been prepared in high yields using thermodynamically controlled dynamic nucleophilic substitution.     

Isothermal kinetics of dehydration of equilibrium swollen poly(acrylic acid) hydrogel

An isothermal dehydration of equilibrium swollen poly(acrylic acid) hydrogel in the temperature range from 306 to 361 K was investigated. The specific parameters connected with shape of the conversion curves were defined. The activation parameters (E, lnA) of the isothermal dehydration of equilibrium swollen poly(acrylic acid) hydrogel were calculated, using Johnson-Mehl-Avrami (JMA), ‘initial rate’ and ’stationary point’ methods. The reaction models for the investigated dehydration are determined using the ‘model-fitting’ method. It was established that both, the reaction model and activation parameters of the hydrogel dehydration were completely different for the isothermal process than for the non-isothermal one. It was found that the increase in dehydration temperature lead to the changes in isothermal kinetic model for the investigated hydrogel dehydration. It was established that the apparent activation energy (E) of hydrogel dehydration is similar to the value of the molar enthalpy of water evaporation.     

Contribution to the analysis of the essential oil of Helichrysum italicum (Roth) G. Don. Determination of ester bonded acids and phenols

The essential oil of Helichrysum italicum (Roth) G. Don (everlasting or Immortelle essential oil) was isolated by hydrodistillation and analysed by GC and GCMS. Forty four compounds were identified. The main components were alpha-pinene(12.8%), 2-methyl-cyclohexyl pentanoate (11.1 %), neryl acetate (10.4%), 1,7-di-epi-alpha-cedrene (6.8%) and other compounds. The oil was fractionated and ester-containing fraction was hydrolysed with KOH/H(2)SO(4). The liberated volatiles were analysed by GC and GC-MS: three phenols and twenty seven volatile carboxylic acids were identified[70% low fatty acids (C(2)-C(5)), 15% C(10)-C(12) acids and 15% other acids]. The main acids were acetic acid (24.3%) propanoic acid (17.2%), 2-methylpropanoic acid (11.4%),dodecanoic acid (8.7%), 2-methylbutanoic acid (8.3%), (Z)-2-methylbutenoic acid(5.1%) and decanoic acid (4.6%). With respect to the identified bonded carboxylic acids,the minimal number of esters in the oil was twenty seven, but their overall quantity was probably larger due to different possible combinations of alcohols with acids to form esters. On the other hand, only six main esters were identified in the oil before fractionation and hydrolysis.     

Malonic acid concentration as a control parameter in the kinetic analysis of the Belousov-Zhabotinsky reaction under batch conditions

The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) < or = [MA]0 < or = 4.30 x 10(-2) mol dm(-3)) in the presence of bromate (6.20 x 10(-2) mol dm(-3)), bromide (1.50 x 10(-5) mol dm(-3)), sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained.     

Substrate specificity of the acyl transferase domains of EpoC from the epothilone polyketide synthase

The production of epothilone mixtures is a direct consequence of the substrate tolerance of the module 3 acyltransferase (AT) domain of the epothilone polyketide synthase (PKS) which utilises both malonyl- and methylmalonyl-CoA extender units. Particular amino acid motifs in the active site of AT domains influence substrate selection for methylmalonyl-CoA (YASH) or malonyl-CoA (HAFH). This motif appears in hybrid form (HASH) in epoAT3 and may represent the molecular basis for the relaxed specificity of the domain. To investigate this possibility the AT domains from modules 2 and 3 of the epothilone PKS were examined in the heterologous DEBS1-TE model PKS. Substitution of AT1 of DEBS1-TE by epoAT2 and epoAT3 both resulted in functional PKSs, although lower yields of total products were observed when compared to DEBS1-TE (2% and 11.5% respectively). As expected, epoAT3 was significantly more promiscuous in keeping with its nature during epothilone biosynthesis. When the mixed motif (HASH) of epoAT3 within the hybrid PKS was mutated to HAFH (indicative of malonyl-CoA selection) it resulted in a non-productive PKS. When this mixed motif was converted to YASH (indicative of methylmalonyl-CoA selection) the selectivity of the hybrid PKS for methylmalonyl-CoA showed no statistically significant increase, and was associated with a loss of productivity.     

Toward observation of single-file diffusion using the tracer zero-length column method

The tracer zero-length column (ZLC) method has been employed to study the diffusion of toluene in one-dimensional ZSM-12 and SAPO-5 zeolites. A significant deviation in the shape of the measured tracer exchange curves from monoexponential behavior was observed for toluene diffusion in both adsorbents in the limit of long-time asymptotes. In contrast, water/ZSM-12 and acetylene/SAPO-5 systems exhibit tracer exchange curves that are close to monoexponential behavior. Monoexponential curves are usually observed for systems obeying normal (Fickian) diffusion. Such diffusion is expected for the latter two systems because the diameters of both sorbates are less than the radii of their corresponding host channels. The differences in the shape of the tracer exchange curves for large and small sorbates can be explained by assuming the occurrence of anomalous, single-file diffusion for large sorbates in narrow, one-dimensional channels.