The mass transfer kinetics in columns packed with Halo-ES shell particles

The average mesopore size of the new Halo-ES-Peptide shell particles is 160 ?, markedly larger than that of the classical Halo shell particles (90 ?). We found that this change causes a considerable decrease of the film mass transfer resistance measured for columns packed with these particles. We analyze data obtained by systematic measurements of the C term of the van Deemter equation for the peptide β-lipotropin (MW = 769 Da), the protein insulin (MW = 5800 Da), and a series of non-retained polystyrene standards (MW = 6400 and 13,200). The improvement in column performance is explained by an increase of the fraction of the external surface area of the shell that allows the entrance of the sample molecules inside the particle. The fraction of the shell surface accessible to a probe controls the rate of its external film mass transfer, i.e. its rate of transfer between the interstitial and the stagnant eluent. Although measurable, the increase in sample diffusivity through the porous shells does not account for the better performance of Halo-ES-peptide columns. Furthermore, the analysis of the HETPs data of small molecules (uracil, acetophenone, toluene, and naphthalene, MW< 150) reveals that the eddy diffusion (A) term of these new columns is 25% lower than that of the classical Halo columns. This result is consistent with the impact of intra-particle diffusivity on the eddy diffusion mechanism in packed columns. As shell diffusivity increases, so does the rate of transfer of sample molecules between the eluent stream-paths flowing through the packed particles and across the column diameter. Dispersion through short-range inter-channel and trans-column eddies is reduced.     

A chromatographic estimate of the degree of surface heterogeneity of reversed-phase liquid chromatography packing materials. II-Endcapped monomeric C18-bonded stationary phase

In a previous report, the heterogeneity of a non-endcapped C30-bonded stationary phase was investigated, based on the results of the measurements of the adsorption isotherms of two neutral compounds (phenol and caffeine) and two ionizable compounds (sodium naphthalene sulfonate and propranololium chloride) by frontal analysis (FA). The same method is applied here for the characterization of the surface heterogeneity of two new brands of endcapped C18-bonded stationary phases (Gemini and Sunfire). The adsorption isotherms of the same four chemicals were measured by FA and the results confirmed by the independent calculation of the adsorption energy distribution (AED), using the expectation-maximization (EM) method. The effect of the length of the bonded alkyl chain was investigated. Shorter alkyl-bonded-chains (C18 versus C30) and the end-capping of the silica surface contribute to decrease the surface heterogeneity under the same experimental conditions (30% methanol, 25 mM NaCl). The AEDs of phenol and caffeine are bimodal with the C18-bonded columns while they are trimodal and quadrimodal, respectively, with a non-endcapped C30-bonded column. The "supersites" (adsorption energy > 20 kJ/mol) found on the C30-Prontosil column and attributed to a cation exchange mechanism completely disappear on the C18-Gemini and C18-Sunfire, probably because the end-capping of the silica surface eliminates most if not all the ionic interactions.     

Detection issues in two-dimensional on-line chromatography

The dilution of analytes during their migration through two-dimensional liquid chromatographic systems was investigated. Simplified equations for the calculation of the dilution factors in the first and second dimension columns were derived considering the variance of the injected sample, the flow rates, the split ratio, the volume of the intermediate sample loop and the sampling time of the first-dimension effluent. The net dilution factor is the product of the dilution factors in the two single dimensions. It is between 200 and 300 in typical two-dimensional liquid chromatographic (2D-LC) separations. These values are less pessimistic than those reported previously [1]. It was shown that the fraction of organic modifier or stronger eluent component in the injected sample has a significant effect on the widths and heights of the eluted peaks. Analytes with high retention factors and high molecular weights are less sensitive toward this effect than those having small retention factors. These results suggest that the optimization of the experimental conditions of two dimension separations must be made from the points of view of both the retention factor and the detector response factor. The frequency of sampling of the eluent of the first-dimension separation does not have a significant effect on the detection limit of a 2D system if the split ratio is adjusted in the ratio of the frequency of sample collection.     

Solvation of uranyl-CMPO complexes in dry vs. humid forms of the [BMI][PF6] ionic liquid. A molecular dynamics study

The solvation of the [UO(2)(NO(3))(CMPO)](+) and [UO(2)(NO(3))(2)(CMPO)(2)] complexes (CMPO = octyl(phenyl)-N,N-diisobutylmethylcarbamoyl phosphine oxide) is investigated by molecular dynamics in the "dry" and "humid" forms of a room temperature ionic liquid (IL) based on the 1-butyl-3-methylimidazolium (BMI(+)) cation and the hexafluorophosphate (PF(6)(-)) anion. The simulations reveal the importance of the solvent anions in "dry" conditions and of water molecules in the "humid" solvent. For the [UO(2)(NO(3))(CMPO)](+) complex, the monodentate vs. bidentate coordination modes of CMPO are compared, and the first solvation shell of uranyl is completed by 1-3 PF(6)(-) anions in the dry IL and by 2-3 water molecules in the humid IL, leading to a total coordination number close to 5. The energy analysis shows that interactions with the IL stabilize the [UO(2)(NO(3))(bi)(CMPO)(mono)](+) form (with bidentate nitrate and monodentate CMPO) in the dry IL and the [UO(2)(NO(3))(mono)(CMPO)(mono)](+) form (with monodentate nitrate and CMPO) in the humid IL. The extracted compound characterized by EXAFS is thus proposed to be the [UO(2)(NO(3))(mono)(CMPO)(mono)(H(2)O)(3)](+) species. Furthermore we compare the [UO(2)(NO(3))(2)(CMPO)(2)] complex in its associated and dissociated forms ([UO(2)(NO(3))(mono)(CMPO)(mono)](+) + CMPO + NO(3)(-)) and discuss the results in the context of uranyl extraction by CMPO to ionic liquids.     

Public Disclosure Programs vs. traditional approaches for environmental regulation: Green goodwill and the policies of the firm

A Public Disclosure Program (PDP) is compared to a traditional environmental regulation (exemplified by a tax/subsidy) in a simple dynamic framework. A PDP aims at revealing the environmental record of firms to the public. This information affects its image (goodwill or brand equity), and ultimately its profit. A firm polluting less than its prescribed target would win consumer’s sympathy and raise its goodwill, whereas it is the other way around when the firm exceeds its emissions quota. The evolution of this goodwill is assumed to depend also on green activities or advertising expenditures. Within this framework, we analyze how a PDP affects the firm’s optimal policies regarding emissions, pricing and advertising as compared to a traditional regulation. We show that advertising acts as a complementary device to pricing and that emissions are increasing in goodwill. The role of a standard or target level for emissions turns out to be totally different under both policy regimes. In the case of a tax/subsidy approach, this target level only acts as constant who increases or decreases profit by a fixed amount, but it does not affect the policy of the firm. On the contrary, if a PDP is implemented, the target value for emissions enters in an important way in the goodwill accumulation mechanism and determines how the firm reacts to the regulation and what is the time path for the economic and environmental variables. Moreover, this value is also crucial to determine the possibility that a PDP is profit improving. A policy implication of this fact is that regulators should be particularly careful in fixing the emission standard when a PDP is applied. The theoretical results are complemented with a numerical illustration.     

Theories egalitaires dans les Langages sur types de graphes

Sans résumé Ce travail doit son origine et son développement, aux préoccupations de recherche qui animent le groupe de “Logique et théorie des catégories,” dirigé par le Professeur A. Preller à l'U.E.R. de Luminy (Université d'Aix-Marseille II). Presented by J. D. Monk.     

A Gelfand duality for compact pospaces

It is well known that the category of compact Hausdorff spaces is dually equivalent to the category of commutative \(C^\star \)-algebras. More generally, this duality can be seen as a part of a square of dualities and equivalences between compact Hausdorff spaces, \(C^\star \)-algebras, compact regular frames and de Vries algebras. Three of these equivalences have been extended to equivalences between compact pospaces, stably compact frames and proximity frames, the fourth part of what will be a second square being lacking. We propose the category of bounded Archimedean \(\ell \)-semi-algebras to complete the second square of equivalences and to extend the category of \(C^\star \)-algebras.     

Repeatability and reproducibility of high concentration data in reversed-phase liquid chromatography. I. Overloaded band profiles on Kromasil-C18

Single-component adsorption-isotherm data were acquired by frontal analysis (FA) for six low-molecular-mass compounds (phenol, aniline, caffeine, theophylline, ethylbenzene and propranolol) on one Kromasil-C18 column, using water-methanol solutions (between 70:30 and 20:80, v/v) as the mobile phase. Propranolol data were also acquired using an acetate buffer (0.2 M) instead of water. The data were modeled for best agreement between calculated and experimental overloaded band profiles. The adsorption energy distribution was also derived and used for the selection of the best isotherm model. Widely different isotherm models were found to model best the data obtained for these compounds, convex upward (i.e. Langmuirian), convex downward (i.e. anti-Langmuirian), and S-shaped isotherms. Using the same sample size for all columns (loading factor, Lf approximately 10%), overloaded band profiles were recorded on four different columns packed with the same batch of Kromasil-C18 and five other columns packed with different batches of Kromasil-C18. These experimental band profiles were compared to the profile calculated from the isotherm measured by FA on the first column. The repeatability as well as the column-to-column and the batch-to-batch reproducibilities of the band profiles are better than 4%.     

Kekulé versus Lewis: When Aromaticity Prevents Electron Pairing and Imposes Polyradical Character

Some conjugated alternant hydrocarbons, of singlet ground state according to Ovchinnikov’s rule, may exhibit strong polyradical character, despite admitting complete pairing of electrons in bond orbitals between adjacent atoms. Typical organizations of this kind are encountered in polycyclic frames supporting two or more extracyclic methylene groups. Lewis bond pairing would require quinonization of six‐membered rings, whereas safeguarding aromaticity proves sufficient to impose ground‐state open‐shell character, that is, the existence of unpaired electrons, providing the number of benzene rings to be quinonized is larger than two. Several examples built as variations around para‐polyphenylene frames are examined through unrestricted DFT (UDFT) calculations, using various methods for spin decontamination of wavefunctions, geometries, and singlet–triplet energy gaps. They all illustrate how it is possible to conceive architectures that can be written with a closed‐shell bond pairing, although they exhibit a large number of unpaired electrons. The same analyses also apply to systems in which quinonization would not kill but only reduce the number of unpaired electrons.     

Synthesis of charged hybrid particles via dispersion polymerization in nonpolar media for color electrophoretic display application

Direct synthesis of charged hybrid particles in non‐polar media has not been widely described in the literature but can lead to many applications such as electrophoretic displays. In this work, we propose a way to synthesize charged hybrid particles within the electrophoretic medium (Toluene or Isopar G) in the presence or not of additives (Charge Control Agent, CCA). The particles synthesis was performed by Nitroxide‐mediated Radical Polymerization (NMRP) via dispersion polymerization in aliphatic hydrocarbon solvents leading to stable chargeable particles with a good size control. Hybrid particles are successfully charged by reaction with functional monomers or addition of CCA to obtain electrophoretic particles. The performance of a dual‐color red/white ink in a display was demonstrated with a test‐cell. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 338–348