Assembly of a supramolecular capsule on a molecular printboard

A molecular capsule based on ionic interactions between two oppositely charged calix[4]arenes, 1 and 2, was assembled both in solution and on a surface. In solution, the formation of the equimolar assembly 1.2 was studied by (1)H NMR, ESI-MS, and isothermal titration calorimetry, giving an association constant (K(a)) of 7.5 x 10(5) M(-1). A beta-cyclodextrin self-assembled monolayer (beta-CD SAM) on gold was used as a molecular printboard to anchor the tetraguanidinium calix[4]arene (2). The binding of tetrasulfonate calix[4]arene 1 was monitored by surface plasmon resonance spectroscopy. Rinsing of the surface with a high ionic strength aqueous solution allows the removal of the tetrasulfonate calix[4]arene (1), while by rinsing with 2-propanol it is possible to achieve the complete desorption of the tetraguanidinium calix[4]arene (2) from the beta-CD SAM. The K(a) for the capsule formation on a surface is 3.5 x 10(6) M(-1), thus comparing well with the K(a) determined in solution.     

Exciton Interactions,Excimer Formation,and [2π+2π] Photodimerization in Nonconjugated Curcuminoid-BF2 Dimers

We describe the synthesis of a series of covalently linked dimers of quadrupolar curcuminoid-BF₂ dyes and the detailed investigation of their solvent-dependent spectroscopic and photophysical properties. In solvents of low polarity, intramolecular folding induces the formation of aggregated chromophores, the UV/Vis absorption spectra of which display the optical signature characteristic of weakly-coupled H-aggregates. The extent of folding and, in turn, of ground-state aggregation is strongly dependent on the nature of the flexible linker. Steady-state and time-resolved fluorescence emission spectroscopies show that the Frenkel exciton relaxes into a fluorescent symmetrical excimer state with a long lifetime. Furthermore, our in-depth studies show that a weakly emitting excimer lies on the pathway toward a photocyclomer. Two-dimensional ¹H NMR spectroscopy and density functional theory (DFT) allowed the structure of the photoproduct to be established. To our knowledge, this represents the first example of a [2π+2π] photodimerization of the curcuminoid chromophore.     

Phytochemical Investigation and Biological Activities of Lantana rhodesiensis

Lantana rhodesiensis Moldenke is a plant widely used to treat diseases, such as rheumatism, diabetes, and malaria in traditional medicine. To better understand the traditional uses of this plant, a phytochemical study was undertaken, revealing a higher proportion of polyphenols, including flavonoids in L. rhodesiensis leaf extract and moderate proportion in stem and root extracts. The antioxidant activity of the extracts was also determined using three different assays: the radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity, the FRAP method (Ferric-reducing antioxidant power) and the β-carotene bleaching test. The anti-malarial activity of each extract was also evaluated using asexual erythrocyte stages of Plasmodium falciparum, chloroquine-sensitive strain 3D7. The results showed that the leaf extract exhibited higher antioxidant and anti-malarial activities in comparison with the stem and root extracts, probably due to the presence of higher quantities of polyphenols including flavonoids in the leaves. A positive linear correlation was established between the phenolic compound content (total polyphenols including flavonoids and tannins; and total flavonoids) and the antioxidant activity of all extracts. Furthermore, four flavones were isolated from leaf dichloromethane and ethyl acetate fractions: a new flavone named rhodescine (5,6,3′,5′-tetrahydroxy-7,4′-dimethoxyflavone) (1), 5-hydroxy-6,7,3′,4′,5′-pentamethoxyflavone (2), 5-hydroxy-6,7,3′,4′-tetramethoxyflavone (3), and 5,6,3′-trihydroxy-7,4′-dimethoxyflavone (4). Their structures were elucidated by ¹H, ¹³CNMR, COSY, HSQC, HMBC, and MS-EI spectral methods. Aside from compound 2, all other molecules were described for the first time in this plant species.     

Sensitivity‐Enhanced 13C‐NMR Spectroscopy for Monitoring Multisite Phosphorylation at Physiological Temperature and pH

Abundant phosphorylation events control the activity of nuclear proteins involved in gene regulation and DNA repair. These occur mostly on disordered regions of proteins, which often contain multiple phosphosites. Comprehensive and quantitative monitoring of phosphorylation reactions is theoretically achievable at a residue‐specific level using ¹H‐¹⁵N NMR spectroscopy, but is often limited by low signal‐to‐noise at pH>7 and T>293 K. We have developed an improved ¹³Cα‐¹³CO correlation NMR experiment that works equally at any pH or temperature, that is, also under conditions at which kinases are active. This allows us to obtain atomic‐resolution information in physiological conditions down to 25 μm . We demonstrate the potential of this approach by monitoring phosphorylation reactions, in the presence of purified kinases or in cell extracts, on a range of previously problematic targets, namely Mdm2, BRCA2, and Oct4.     

A model for describing the thermodynamics of multivalent host-guest interactions at interfaces

A model has been described for interpreting the binding of multivalent molecules to interface-immobilized monovalent receptors through multiple, independent interactions. It is based on the concept of effective concentration, C(eff), which has been developed before for multivalent binding in solution and which incorporates effects of lengths and flexibilities of linkers between interacting sites. The model assumes: (i). the interactions are independent, (ii). the maximum number of interactions, p(max), is known, (iii). C(eff) is estimated from (simple) molecular models. Simulations of the thermodynamics and kinetics of multivalent host-guest binding to interfaces have been discussed, and competition with a monovalent competitor in solution has been incorporated as well. The model was successfully used to describe the binding of a divalent guest to self-assembled monolayers of a cyclodextrin host. The adsorption data of more complex guest-functionalized dendrimers, for which p(max) was not known beforehand, was interpreted as well. Finally, it has been shown that the model can aid to deconvolute contributions of multivalency and cooperativity to stability enhancements observed for the adsorption of multivalent molecules to interfaces.     

IMP321 (sLAG-3), an immunopotentiator for T cell responses against a HBsAg antigen in healthy adults: a single blind randomised controlled phase I study

Background  

LAG-3 (CD223) is a natural high affinity ligand for MHC class II. The soluble form (sLAG-3) induces maturation of monocyte-derived dendritic cells in vitro and is used as a potent Th1-like immune enhancer with many antigens in animal models. To extend this observation to human, a proof of concept study was conducted with a clinical-grade sLAG-3, termed IMP321, coinjected with alum-non-absorbed recombinant hepatitis B surface antigen.     

Green synthesis of para-Menthane-3,8-diol from Eucalyptus citriodora: Application for repellent products

A simple and efficient method was developed for the synthesis of para-Menthane-3,8-diol (PMD), a well-known repellent active against mosquitoes, from Eucalyptus citriodora essential oil by a treatment of citric acid in a biphasic medium (H₂O/essential oil). The E. citriodora contains as main component (+)-citronellal (74% in the present case), which cyclises (Prins reaction) to form cis/trans PMD isomers. As an example, an emulsion containing an aqueous solution of 7% citric acid and E. citriodora oil at 50°, conducted after 15 h stirring to 82% conversion of (+)-citronellal with a selectivity of 80% with the remaining presence of monoterpenes and sesquiterpenes in the medium. Investigations of lasting protection on human volunteers are carried out using a cage test bioassay protocol and Aedes aegypti mosquitoes. At 20% in ⁱPrOH, the new reaction mixture showed a complete protection of 303 min compared to 22 min with the pure essential oil. The modified oil was compared with N,N-diethyl-m-methylbenzamide (DEET), the most popular active used in repellent formulations. Thermogravimetric analyses (TGA) of E. citriodora, the modified oil, PMD, DEET, and (+)-citronellal were performed and showed a slow evaporation rate for PMD and DEET as well as for the modified oil, which may explain their long lasting protection action.     

Investigation of operational parameters for an industrial CFB combustor of coal, biomass and sludge

The combustion of coal and/or biomass （sludge, wood waste, RDF, etc.） in a circulating fluidized bed has been a commercial topper for over 20 years, and references to principles and applications are numerous and widespread although few data are presented concerning the operation of large scale CFB-units. The authors studied the CFB-combustion at UPM-Kymmene （Ayr）, a major paper mill relying for its steam production upon the combustion of coal （80-85 %）, wood bark （5-10%） and wastewater treatment sludge （5-10%）. The maximum capacity of the CFB is 58 MWth. A complete diagnostic of the operation was made, and additional tests were performed to assess the operating mode. The plant schematics, relevant dimensions and process data are given. To assess the operation of the UPM-CFB, it is important to review essential design parameters and principles of CFB combustors, which will be discussed in detail to include required data, heat balance and flowrates, operating versus transport velocity, kinetics and conversion （including the possible effect of the Bouduard reaction if carbon is present）. Since the residence time in the riser and the cyclone efficiency determine the burnout of circulating fuel-particles, the UPM-CFB was subjected to a stimulus response technique using nickel oxide as tracer. Results illustrate the efficiency of the cyclone separation and the number of recycle loops for particles of a given size. Results will also be used to assess the cyclone operation and efficiency and to comment upon expected and measured carbon conversion.     

Generation of Silicone Poly‐HIPEs with Controlled Pore Sizes via Reactive Emulsion Stabilization

Macrocellular silicone polymers are obtained after solidification of the continuous phase of a poly(dimethylsiloxane) emulsion, which contains poly(ethylene glycol) drops of sub‐millimetric dimensions. Coalescence of the liquid template emulsion is prohibited by a reactive blending approach. The relationship is investigated in detail between the interfacial properties and the emulsion stability, and micro‐ and millifluidic techniques are used to generate macrocellular polymers with controlled structural properties over a wider range of cell sizes (0.2–2 mm) and volume fractions of the continuous phase (0.1%–40%). This approach could easily be transferred to a wide range of polymeric systems.