Polymer structure and the compensation effect of the diffusion pre-exponential factor and activation energy of a permeating solute

In the present work, the relation between the pre-exponential factor and the apparent activation energy of diffusion, ln D(0) = alpha + betaE(D), so-called compensation effect, is re-examined and critically discussed for diffusion of gases in rubbery and glassy polymers. In principle, the above equation could be derived from the enthalpy-entropy compensation in the framework of the transition state theory. However, one should consider the influence of the jump length term contained in the pre-exponential factor, which may be affected by permeating species and polymer properties. We found that parameter alpha depends on penetrant size and polymer properties, such as local chain mobility and free volume. This can be interpreted by the fact that the jump length is affected by both penetrant and polymer properties. Finally, methods for estimating the jump length are discussed.     

Simultaneous distillation-extraction of high-value volatile compounds from Cistus ladanifer L

The present paper describes a procedure to isolate volatiles from rock-rose (Cistus ladanifer L.) using simultaneous distillation-extraction (SDE). High-value volatile compounds (HVVC) were selected and the influence of the extraction conditions investigated. The effect of the solvent nature and extraction time on SDE efficiency was studied. The best performance was achieved with pentane in 1 h operation. The extraction efficiencies ranged from 65% to 85% and the repeatability varied between 4% and 6% (as a CV%).The C. ladanifer SDE extracts were analysed by headspace solid phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The HS-SPME sampling conditions such as fiber coating, temperature, ionic strength and exposure time were optimized. The best results were achieved with an 85 μm polyacrylate fiber for a 60 min headspace extraction at 40 °C with 20% (w/v) of NaCl. For optimized conditions the recovery was in average higher than 90% for all compounds and the intermediate precision ranged from 4 to 9% (as CV %). The volatiles α-pinene (22.2 mg g⁻¹ of extract), 2,2,6-trimethylcyclohexanone (6.1 mg g⁻¹ of extract), borneol (3.0 mg g⁻¹ of extract) and bornyl acetate (3.9 mg g⁻¹ of extract) were identified in the SDE extracts obtained from the fresh plant material.     

Group 4 complexes of a new [OSSO]-type dianionic ligand. Coordination chemistry and preliminary polymerization catalysis studies

A straightforward synthesis of a new type of tetradentate dianionic [OSSO]-type ligand is described. This ligand features an ethylenedithiol core bridged via methylene groups to substituted phenols, thus representing an S analogue of the [ONNO]-type Salan ligands. The [OSSO]H2 ligand precursor reacted with titanium(IV) isopropoxide and with zirconium(IV) tert-butoxide to give the corresponding [OSSO]-M(OR)2 complexes, which formed as single C2-symmetric isomers but were fluxional according to variable-temperature NMR. An X-ray structure of [OSSO]-Zr(O-t-Bu)2 supported the fac-fac wrapping mode of the ligand. The dibenzyl complex [OSSO]-Zr(bn)2 that was obtained by a reaction between the ligand precursor and tetrabenzylzirconium was found to be an active 1-hexene polymerization catalyst upon activation with B(C6F5)3, leading to a stereoirregular polymer despite its C2 symmetry.     

Mixed unsymmetric oxadiazoline and/or imine platinum(II) complexes

Iminoacylation of acetone oxime Me(2)C[double bond, length as m-dash]NOH upon reaction with trans-[PtCl(2)(NCCH(2)CO(2)Me)(2)] and [2 + 3] cycloaddition of acyclic nitrone (-)O(+)N(Me) = C(H)(C(6)H(4)Me-4) to a nitrile ligand in lead to the formation of mono-imine trans-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] [imine-a = NH[double bond, length as m-dash]C(CH(2)CO(2)Me)ON = CMe(2)] and mono-oxadiazoline trans-[PtCl(2)(oxadiazoline-a)(NCCH(2)CO(2)Me)] [oxadiazoline-a = [upper bond 1 start]N[double bond, length as m-dash]C(CH(2)CO(2)Me)ON(Me)C[upper bond 1 end](H)(C(6)H(4)Me-4)] unsymmetric mixed ligand complexes, respectively, as the main products. Reactions of or with acetone oxime , cyclic nitrone (-)O(+)N = CHCH(2)CH(2)C[upper bond 1 end]Me(2) or N,N-diethylhydroxylamine give access, in moderate to good yields, to the unsymmetric mixed ligand oxadiazoline and/or imine complexes trans-[PtCl(2)(oxadiazoline-a)(imine-a)] , trans-[PtCl(2)(oxadiazoline-a)(oxadiazoline-b)] [oxadiazoline-b = [upper bond 1 start]N[double bond, length as m-dash]C(CH(2)CO(2)Me)O[lower bond 1 start]NC[upper bond 1 end](H)CH(2)CH(2)C[lower bond 1 end]Me(2)], trans-[PtCl(2)(imine-a)(imine-b)] [imine-b = NH = C(CH(2)CO(2)Me)ONEt(2)] or trans-[PtCl(2)(imine-a)(oxadiazoline-b)] . The cis mono-imine mixed ligand complex cis-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] is the major product from the reaction of cis-[PtCl(2)(NCCH(2)CO(2)Me)(2)] with the oxime , while the di-imine compound cis-[PtCl(2)(imine-a)(2)] is a minor product. Reaction of cis-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] with N,N-diethylhydroxylamine or the cyclic nitrone affords, in good yields, the unsymmetric mixed ligand complexes cis-[PtCl(2)(imine-a)(imine-b)] or cis-[PtCl(2)(imine-a)(oxadiazoline-b)] , respectively. All these complexes were characterized by elemental analyses, IR and (1)H, (13)C and (195)Pt NMR spectroscopies, and FAB(+)-MS. The X-ray structural analysis of trans-[PtCl(2){NH=C(CH(2)CO(2)Me)ON=CMe(2)}(NCCH(2)CO(2)Me)] is also reported.     

Importance sampling algorithms for first passage time probabilities in the infinite server queue

This paper applies importance sampling simulation for estimating rare event probabilities of the first passage time in the infinite server queue with renewal arrivals and general service time distributions. We consider importance sampling algorithms which are based on large deviations results of the infinite server queue, and we consider an algorithm based on the cross-entropy method, where we allow light-tailed and heavy-tailed distributions for the interarrival times and the service times. Efficiency of the algorithms is discussed by simulation experiments.     

The Orthogonal Subcategory Problem and the Small Object Argument

A classical result of P. Freyd and M. Kelly states that in “good” categories, the Orthogonal Subcategory Problem has a positive solution for all classes of morphisms whose members are, except possibly for a subset, epimorphisms. We prove that under the same assumptions on the base category and on , the generalization of the Small Object Argument of D. Quillen holds—that is, every object of the category has a cellular -injective weak reflection. In locally presentable categories, we prove a sharper result: a class of morphisms is called quasi-presentable if for some cardinal λ every member of the class is either λ-presentable or an epimorphism. Both the Orthogonal Subcategory Problem and the Small Object Argument are valid for quasi-presentable classes. Surprisingly, in locally ranked categories (used previously to generalize Quillen’s result), this is no longer true: we present a class of morphisms, all but one being epimorphisms, such that the orthogonality subcategory is not reflective and the injectivity subcategory Inj is not weakly reflective. We also prove that in locally presentable categories, the injectivity logic and the Orthogonality Logic are complete for all quasi-presentable classes. Financial support by Centre for Mathematics of University of Coimbra and by School of Technology of Viseu is acknowledged by the third author.     

Method validation for the simultaneous determination of fecal sterols in surface waters by gas chromatography-mass spectrometry

Besides microbiological methods, fecal pollution of surface waters is estimated by gas chromatographic (GC) determination of sterols present in human and animal sewage effluents. The most frequently used biomarkers for the evaluation of contamination levels include coprostanol, cholesterol, dihydrocholesterol, stigmasterol, beta-sitosterol, and stigmastanol. Although several GC techniques are used to measure these compounds in aquatic systems, the analytical performance of GC-mass spectrometric (MS) determination of these sterols has not been systematically characterized. Therefore, the aim of this work is to validate a simple and rapid GC-MS method for the simultaneous analysis of six sterols, considering all parameters and requirements defined by Good Laboratory Practice. Following liquid-liquid extraction of spiked surface water samples, the extracts are silylated and analyzed by GC-MS. The method is evaluated for linearity and limits of detection and quantitation, as well as for precision, extraction efficiency, and stability. The assay is linear up to 160 ng; the limits of detection and quantitation are 5-10 ng and 20 ng, respectively. The within- and between-day precision ranged from 1% to 9% and 1% to 16%, respectively. The extraction efficiency was 65-80%. The stability studies indicate that the sterols in surface water samples begin to degrade after 24 h of refrigerated storage. However, three freeze/thaw cycles could be performed without their decomposition. The method is applied to the analysis of surface water and wastewater samples. The technical advantages make this GC-MS analysis suitable for routine environmental monitoring of fecal pollution in aquatic systems.     

Ab initio potential-energy surface and rovibrational states of the HCN-HCl complex

A four-dimensional intermolecular potential-energy surface has been calculated for the HCN-HCl complex, with the use of the coupled cluster method with single and double excitations and noniterative inclusion of triples. Data for more than 13,000 geometries were represented by an angular expansion in terms of coupled spherical harmonics; the dependence of the expansion coefficients on the intermolecular distance R was described by the reproducing kernel Hilbert space method. The global minimum with De=1565 cm(-1) and Re=7.47a0 has a linear HCN-HCl hydrogen-bonded structure with HCl as the donor. A secondary hydrogen-bonded equilibrium structure with De=564 cm(-1) and Re=8.21a0 has a T-shaped geometry with HCN as the donor and the acceptor HCl molecule nearly perpendicular to the intermolecular axis. This potential surface was used in a variational approach to compute a series of bound states of the isotopomers HCN-H35Cl, DCN-H35Cl, and HCN-H37Cl for total angular momentum J=0,1,2 and spectroscopic parities e, f. The results could be analyzed in terms of the approximate quantum numbers of a linear polyatomic molecule with two coupled bend modes, plus a quantum number for the intermolecular stretch vibration. They are in good agreement with the recent high resolution spectrum of Larsen et al. [Phys. Chem. Chem. Phys. 7, 1953 (2005)] in the region of 330 cm(-1) corresponding to the HCl libration. The (partly anomalous) effects of isotopic substitutions on the properties of the complex were explained with the aid of the calculations.     

Distonoid ions

By Yates, Bouma, and Radom's definition, distonic radical ions are those formally arising by ionization of diradicals or zwitterionic molecules (including ylides). These ions differ, therefore, from conventional radical ions by displaying the charge site and unpaired electron site (spin) localized mandatorily on separate atoms or group of atoms; that is, these sites are separated in all of their major resonance forms. Many conventional radical ions with a major resonance form in which charge and spin sites reside formally on the same atom or group of atoms display, however, high degree of discretionary (non-mandatory) charge-spin separation. By analogy with the metal/metalloid terminology, we propose that these distonic-like radical ions be classified as distonoid ions. Radical ions would, therefore, be divided into three sub-classes: conventional, distonic, and distonoid ions. B3LYP/6-311 + G(d,p) calculations for a proof-of-principle set of radical cations are used to demonstrate the existence of many types of distonoid ions with a high degree of discretionary charge-spin separation. Reliable calculations are indispensable for probing distonoid ions, since an ion that was expected to be distonoid (by the analysis of its resonance forms) is shown by the calculations to display a characteristic conventional-ion electronic distribution. Similarly to many distonic radical ions, and in sharp contrast to a conventional radical ion (ionized 1,4-dioxane), the gas-phase intrinsic bimolecular reactivity with selective neutrals of a representative distonoid ion, ionized 2-methylene 1,3-dioxolane, is found to include dual ion-radical type reactions.