Modification of the surface adsorption properties of alumina-supported Pd catalysts for the electrocatalytic hydrogenation of phenol

The electrocatalytic hydrogenation (ECH) of phenol has been studied using palladium supported on gamma-alumina (10% Pd-Al2O3) catalysts. The catalyst powders were suspended in aqueous supporting electrolyte solutions containing methanol and short-chain aliphatic acids (acetic acid, propionic acid, or butyric acid) and were dynamically circulated through a reticulated vitreous carbon cathode. The efficiency of the hydrogenation process was measured as a function of the total electrolytic charge and was compared for different types of supporting electrolyte and for various solvent compositions. Our results show that these experimental parameters strongly affect the overall ECH efficiency of phenol. The ECH efficiency and yields vary inversely with the quantity of methanol present in the electrolytic solutions, whereas the presence of aliphatic carboxylic acids increased the ECH efficiency in proportion to the chain length of the specific acids employed. In all cases, ECH efficiency was directly correlated with the adsorption properties of phenol onto the Pd-alumina catalyst in the studied electrolyte solution, as measured independently using dynamic adsorption isotherms. It is shown that the alumina surface binds the aliphatic acids via the carboxylate terminations and transforms the catalyst into an organically functionalized material. Temperature-programmed mass spectrometry analysis and diffuse-reflectance infrared spectroscopy measurements confirm that the organic acids are stably bound to the alumina surface below 200 degrees C, with coverages that are independent of the acid chain length. These reproducibly functionalized alumina surfaces control the adsorption/desorption equilibrium of the target phenol molecules and allow us to prepare new electrocatalytic materials to enhance the efficiency of the ECH process. The in situ grafting of specific aliphatic acids on general purpose Pd-alumina catalysts offers a new and flexible mechanism to control the ECH process to enhance the selectivity, efficiency, and yields according to the properties of the specific target molecule.     

Adsorption-induced fibronectin aggregation and fibrillogenesis

Fibronectin (Fn), a high molecular weight glycoprotein, is a central element of extracellular matrix architecture that is involved in several fundamental cell processes. In the context of bone biology, little is known about the influence of the mineral surface on fibronectin supramolecular assembly. We investigate fibronectin morphological properties induced by its adsorption onto a model mineral matrix of hydroxyapatite (HA). Fibronectin adsorption onto HA spontaneously induces its aggregation and fibrillation. In some cases, fibronectin fibrils are even found connected into a dense network that is close to the matrix synthesized by cultured cells. Fibronectin adsorption-induced self-assembly is a time-dependant process that is sensitive to bulk concentration. The N-terminal domain of the protein, known to be implicated in its self-association, does not significantly inhibit the protein self-assembly while increasing ionic strength in the bulk alters both aggregation and fibrillation. The addition of a non-ionic surfactant during adsorption tends to promote aggregation with respect to fibrillation. Ultimately, fibronectin fibrils appear to be partially structured like amyloid fibrils as shown by thioflavine T staining. Taken together, our results suggest that there might be more than one single organization route involved in fibronectin self-assembly onto hydroxyapatite. The underlying mechanisms are discussed with respect to Fn conformation, Fn/surface and Fn/Fn interactions, and a model of fibronectin fibrillogenesis onto hydroxyapatite is proposed.     

First approach to the use of liquid crystal elastomers for chemical sensors

Liquid crystalline thin films elastomers that are able to bind pesticides have been developed. The synthesis involves grafting mesogen and crosslinkable groups on a polysiloxane chain in the presence of a template molecule. The molecular imprinted material is obtained after thin film deposition, UV crosslinking and washing. Experiments of readsorption of pesticide are presented. Development of a multisensor platform based on thermal and capacitive sensors is described and tests of deposition of the polymer film are presented.     

Simple model for active nematics: quasi-long-range order and giant fluctuations

We propose a simple microscopic model for active nematic particles similar in spirit to the Vicsek model for self-propelled polar particles. In two dimensions, we show that this model exhibits a Kosterlitz-Thouless-like transition to quasi-long-range orientational order and that in this nonequilibrium context, the ordered phase is characterized by giant density fluctuations, in agreement with the predictions of Ramaswamy et al.     

Flags of almost affine codes and the two-party wire-tap channel of type II

We describe a two-party wire-tap channel of type II in the framework of almost affine codes. Its cryptological performance is related to some relative profiles of a pair of almost affine codes. These profiles are analogues to relative generalized Hamming weights in the linear case.     

Synthesis of complex oligosaccharides by using a mutated (1,3)-beta-D-glucan endohydrolase from barley

Complex oligosaccharides with newly formed (1,3)-beta-glycosidic linkages were obtained in good to excellent yields when substituted or unsubstituted alpha-laminaribiosyl fluorides, acting as donors, were condensed onto mono- and disaccharide beta-D-hexopyranoside acceptors by using a (1,3)-beta-D-glycosynthase. These linear and branched (1,3)-beta-linked oligosaccharides could prove to be important in a range of medical, pharmaceutical, and agricultural applications. Furthermore, the observation that the (1,3)-beta-D-glucan glycosynthase accommodates (1,3)-, (1,4),- and (1,6)-beta-oligosaccharides in its acceptor subsites suggests novel, yet unexpected physiological roles for the wild type (1,3)-beta-D-glucan endohydrolase from higher plants.     

Homogenization in open sets with holes

Let Q^r be a cylindrical bar with r cylindrical cavities having generators parallel to those of Q^r. Let Ω be the cross-section of the bar, Ω1 the cross-section of the domain occupied by the material and $\text{Ω}{}^{\mathrm{i}}\text{(i = 1,…, r)}$ the cross- sections of the cavities:

$\text{Ω}\text{?}{}^{\mathrm{i}}\text{? Ω}\text{Ω}\text{?}{}^{\mathrm{i}}\text{∩}\text{Ω}\text{?}{}^{\mathrm{k}}\text{= φ, i ≠ k}$

. The study of the elastic torsion of this bar leads to the following problem [see 2., 3., 267–320)]:

$\text{Δ?}{}_{\mathrm{r}}\text{+ 2μα = 0 in Ω1}$

$\text{?}{}_{\mathrm{r¦?\Omega }}\text{= 0}$

(1)

$\text{?}{}_{\mathrm{r}}\text{=}\text{constant on}\text{?Ω}{}^{\mathrm{i}}\text{; i = 1,…, r}$

where μ is the shear modulus of the material, α is the angle of twist and $\text{?}{}_{\mathrm{r}}$ represents the stress function. In this paper the problem (1) with an increasing number of holes which are distributed periodically is considered. One would like to know if $\text{?}{}_{\mathrm{r}}$ has a limit $\text{?}{}_{\mathrm{\infty }}\text{as}\text{r → + ∞}$, and if so, the equation satisfied by this limit. This is an “homogenization” problem — the heterogeneous bar Q^r is replaced by a homogeneous one, the response of which under torsion approximates as closely as possible that of Q^r. A more general problem will be studied and the case of elastic torsion will be obtained as an application. The proof uses the energy method [see Lions (Collège de France, 1975–1977), Tartar (Collège de France, 1977)] and extension theorems. A related problem is the homogenization of a perforated plate [cf. Duvaut (to appear)].     

Speciation and bioavailability of selenium in yeast-based intervention agents used in cancer chemoprevention studies

This study investigated the speciation and bioavailability of selenium in yeast-based intervention agents from multiple manufacturers from several time points. Sources of selenized yeast included Nutrition 21 (San Diego, CA), which supplied the Nutritional Prevention of Cancer (NPC) Trial from 1981-1996; Cypress Systems (Fresno, CA; 1997-1999); and Pharma Nord (Vejle, Denmark; 1999-2000), which supplied the Prevention of Cancer by Intervention by Selenium (PRECISE) Trial pilot studies. The low-molecular-selenium species were liberated from the samples by proteolytic hydrolysis followed by separation by ion exchange liquid chromatography and detection by inductively coupled plasma-mass spectrometry. The results for the NPC tablets showed that selenomethionine, together with 3 unidentified selenium compounds, were predominant in the sample hydrolysates. The relative amounts of the 4 selenium species varied (p < 0.05) among several of the 7 tablet batches used during the course of the NPC Trial. In comparison, 5 batches of more recently produced selenized yeasts, which were used as a source of selenium in the PRECISE and other trials, contained less of the unknown compounds and more selenomethionine at 54-60% of the total selenium in the yeasts. One batch of yeast, however (from 1985), which originated from the same producer as the yeast used in the NPC tablets, contained only 27% of selenium in the sample as selenomethionine. Human subjects receiving 200 microg selenium/day in the UK PRECISE Pilot Trial showed a higher concentration (p < 0.01) and higher increase from baseline in plasma selenium than did the same dosage used in the NPC Trial. Differences in intake, speciation, or bioavailability of selenium from the yeast-based supplements in the population groups studied may explain this. Furthermore, the selenium concentration in whole blood from the Danish PRECISE Pilot Trial was higher (p < 0.001) than that obtained with synthetic L-selenomethionine in a comparable group of Danes, both groups having been treated with 300 microg selenium/day.