Ru-Containing Polymeric Catalysts for Cellulose Conversion to Polyols

In this paper Ru-containing catalysts based on hypercrosslinked polystyrene (MN-270) and its functional analogues (MN-100 and MN-500) were studied for the first time in cellulose hydrolytic hydrogenation. The catalysts were characterized using transmission electron microscopy (TEM), high resolution TEM, and porosity measurements. Catalytic studies demonstrated that the catalyst containing 1.0 % Ru and based on MN-270 is the most active. The total yield of sorbitol and mannitol was 50 % on the average at 85 % cellulose conversion.     

Differences in the carotenoid content of ketchups and gazpachos through HPLC/ESI(Li(+) )-MS/MS correlated with their antioxidant capacity

BACKGROUND: Carotenoids are important antioxidant compounds in the human diet. Owing to their constrained polyene structure, carotenoids can exist in cis and trans isomeric forms that can be difficult to differentiate in natural samples. In ketchups and gazpachos, all‐trans isomeric forms are predominant. However, during thermal processing, cis isomers are formed. Therefore the determination of carotenoid isomers is required for the assessment of the nutritional value of foods. RESULTS: The main carotenoid found in ketchups was trans‐lycopene, whereas in gazpachos a higher contribution to the total carotenoid content was made by other carotenoids such as 5‐, 9‐ and 13‐cis‐lycopene, lutein, β‐carotene and α‐carotene. Ketchups exhibited the highest lipophilic antioxidant content owing to their higher content of trans‐lycopene, the main carotenoid in tomatoes. CONCLUSION: Direct analysis of carotenoids by electrospray ionisation mass spectrometry (ESI‐MS) often produces poor results requiring offline time‐ and sample‐consuming derivatisation techniques. Therefore in this work a simple ESI‐MS approach is described for the direct analysis of carotenoids in ketchups and gazpachos using the post‐column addition of lithium chloride to promote the cationisation of carotenoids. To the best of the authors' knowledge, this paper presents for the first time the identification of 5‐, 9‐ and 13‐cis‐lycopene in ketchups and gazpachos. Copyright © 2012 Society of Chemical Industry     

Synthesis and Biological Evaluation of Papain‐Family Cathepsin L‐Like Cysteine Protease Inhibitors Containing a 1,4‐Benzodiazepine Scaffold as Antiprotozoal Agents

Novel papain‐family cathepsin L‐like cysteine protease inhibitors endowed with antitrypanosomal and antimalarial activity were developed, through an optimization study of previously developed inhibitors. In the present work, we studied the structure–activity relationships of these derivatives, with the aim to develop new analogues with a simplified and more synthetically accessible structure and with improved antiparasitic activity. The structure of the model compounds was significantly simplified by modifying or even eliminating the side chain appended at the C3 atom of the benzodiazepine scaffold. In addition, a simple methylene spacer of appropriate length was inserted between the benzodiazepine ring and the 3‐bromoisoxazoline moiety. Several rhodesain and falcipain‐2 inhibitors displaying single‐digit micromolar or sub‐micromolar antiparasitic activity against one or both parasites were identified, with activities that were one order of magnitude more potent than the model compounds.     

N‐Benzyl‐4‐((heteroaryl)methyl)benzamides: A New Class of Direct NADH‐Dependent 2‐trans Enoyl–Acyl Carrier Protein Reductase (InhA) Inhibitors with Antitubercular Activity

Isoniazid (INH) remains one of the cornerstones of antitubercular chemotherapy for drug‐sensitive strains of M. tuberculosis bacteria. However, the increasing prevalence of multidrug‐resistant (MDR) and extensively drug‐resistant (XDR) strains containing mutations in the KatG enzyme, which is responsible for the activation of INH into its antitubercular form, have rendered this drug of little or no use in many cases of drug‐resistant tuberculosis. Presented herein is a novel family of antitubercular direct NADH‐dependent 2‐trans enoyl–acyl carrier protein reductase (InhA) inhibitors based on an N‐benzyl‐4‐((heteroaryl)methyl)benzamide template; unlike INH, these do not require prior activation by KatG. Given their direct InhA target engagement, these compounds should be able to circumvent KatG‐related resistance in the clinic. The lead molecules were shown to be potent inhibitors of InhA and showed activity against M. tuberculosis bacteria. This new family of inhibitors was found to be chemically tractable, as exemplified by the facile synthesis of analogues and the establishment of structure–activity relationships. Furthermore, a co‐crystal structure of the initial hit with the enzyme is disclosed, providing valuable information toward the design of new InhA inhibitors for the treatment of MDR/XDR tuberculosis.     

Self-assembly of iron oxide-poly(ethylene glycol) core-shell nanoparticles at liquid-liquid interfaces

Nanoparticles (NPs) play an increasingly important role in the fabrication of functional advanced materials. Two major steps need to be carried out in order to achieve control of the material properties. First of all, the properties of the single NPs have to be under control, especially in relation to colloidal stability; aggregation and corrosion negate all the benefits associated to the nanoscopic dimensions. Secondly, the assembly process has to be controlled to achieve a material with the desired properties. We propose here to use stabilized ceramic NPs consisting of a magnetite core, coated by a poly(ethylene glycol) (PEG) shell and study their assembly at polar/ non-polar liquid interfaces, en route to fabricating functional NP membranes. These NPs show extraordinary stability in aqueous solutions achieved by anchoring linear PEG chains through an end-terminating nitroDOPA group to their surface. Furthermore, the core and shell sizes of these NPs can be independently varied with ease. We first describe the details of the NP synthesis and stabilization in bulk solutions, discussing the PEG molecular weight needed to achieve bulk stability. Subsequently, we demonstrate self-assembly of these particles at liquid-liquid interfaces (SALI) into monolayers of stable properties. SALI has been chosen as path for the assembly given its suitability for fabricating two-dimensional materials. We report here results from pendant drop tensiometry which illustrate the kinetics of NP adsorption at the liquid-liquid interface and highlight the role played by the molecular weight of the PEG shell in the interfacial assembly. In particular we show that the requisites to ensure particle stability at a liquid interface are more stringent compared to the bulk case.     

Cellular Integrin α5β1 and Exosomal ADAM17 Mediate the Binding and Uptake of Exosomes Produced by Colorectal Carcinoma Cells

Approximately 25% of colorectal cancer (CRC) patients develop peritoneal metastasis, a condition associated with a bleak prognosis. The CRC peritoneal dissemination cascade involves the shedding of cancer cells from the primary tumor, their transport through the peritoneal cavity, their adhesion to the peritoneal mesothelial cells (PMCs) that line all peritoneal organs, and invasion of cancer cells through this mesothelial cell barrier and underlying stroma to establish new metastatic foci. Exosomes produced by cancer cells have been shown to influence many processes related to cancer progression and metastasis. In epithelial ovarian cancer these extracellular vesicles (EVs) have been shown to favor different steps of the peritoneal dissemination cascade by changing the functional phenotype of cancer cells and PMCs. Little is currently known, however, about the roles played by exosomes in the pathogenesis and peritoneal metastasis cascade of CRC and especially about the molecules that mediate their interaction and uptake by target PMCs and tumor cells. We isolated exosomes by size−exclusion chromatography from CRC cells and performed cell-adhesion assays to immobilized exosomes in the presence of blocking antibodies against surface proteins and measured the uptake of fluorescently-labelled exosomes. We report here that the interaction between integrin α5β1 on CRC cells (and PMCs) and its ligand ADAM17 on exosomes mediated the binding and uptake of CRC-derived exosomes. Furthermore, this process was negatively regulated by the expression of tetraspanin CD9 on exosomes.     

Palladium‐nanoparticle intercalated vermiculite for selective hydrogenation of α,β‐unsaturated aldehydes

Palladium nanoparticles were generated in the interlamellar region of swelling 2:1 type vermiculite clay using an adsorption excess isotherm. An adsorption excess isotherm was constructed for vermiculite after exchanging the exchangeable Na⁺ ions in the interlamellar region using a binary liquid mixture (ethanol:toluene). Based on adsorption excess isotherm, 1% w/w palladium was intercalated into the interlamellar space of vermiculite. The Pd‐intercalated vermiculite was characterized by X‐ray diffraction, transmission electron microscopy and atomic absorption spectroscopy. The 1% w/w Pd‐intercalated vermiculite was tested for its catalytic activity towards selective hydrogenation reactions involving some α,β‐unsaturated carbonyl compounds using a pulse reactor and its catalytic activity was compared with commercial 1% Pd/C. The intercalated catalyst was found to be very selective towards the desired product of unsaturated alcohols. Copyright © 2007 Society of Chemical Industry