Excess thermodynamics properties of propyl propanoate+hexane+cyclohexane at 298.15 K

Summary In this paper we present excess molar volumes and excess molar enthalpies of binary and ternary mixtures containing propyl propanoate, hexane and cyclohexane as components at 298.15 K. Excess molar volumes were calculated from the density of the pure liquids and mixtures. The density was measured using an Anton Paar DMA 60/602 vibrating-tube densimeter. Excess molar enthalpies were obtained using a Calvet microcalorimeter     

Nannocystin A: an Elongation Factor 1 Inhibitor from Myxobacteria with Differential Anti‐Cancer Properties

Cultivation of myxobacteria of the Nannocystis genus led to the isolation and structure elucidation of a class of novel cyclic lactone inhibitors of elongation factor 1. Whole genome sequence analysis and annotation enabled identification of the putative biosynthetic cluster and synthesis process. In biological assays the compounds displayed anti‐fungal and cytotoxic activity. Combined genetic and proteomic approaches identified the eukaryotic translation elongation factor 1α (EF‐1α) as the primary target for this compound class. Nannocystin A ( 1 ) displayed differential activity across various cancer cell lines and EEF1A1 expression levels appear to be the main differentiating factor. Biochemical and genetic evidence support an overlapping binding site of 1 with the anti‐cancer compound didemnin B on EF‐1α. This myxobacterial chemotype thus offers an interesting starting point for further investigations of the potential of therapeutics targeting elongation factor 1.     

Assessment and formation mechanism of laser-induced periodic surface structures on polymer spin-coated films in real and reciprocal space

In this work we evaluate the potential of grazing incidence X-ray scattering techniques in the investigation of laser-induced periodic surface structures (LIPSSs) in a series of strongly absorbing model spin-coated polymer films which are amorphous, such as poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(carbonate bisphenol A), and in a weaker absorbing polymer, such as semicrystalline poly(vinylidene fluoride), over a narrow range of fluences. Irradiation was performed with pulses of 6 ns at 266 nm, and LIPSSs with period lengths similar to the laser wavelength and parallel to the laser polarization direction are formed by devitrification of the film surface at temperatures above the characteristic glass transition temperature of the polymers. No crystallization of the surface is induced by laser irradiation, and crystallinity of the material prevents LIPSS formation. The structural information obtained by both atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS) correlates satisfactorily. Comparison of experimental and simulated GISAXS patterns suggests that LIPSSs can be well described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice.     

Molecularly imprinted polymer grafted to porous polyethylene frits: a new selective solid-phase extraction format

In this paper, a novel format for selective solid-phase extraction based on a molecularly imprinted polymer (MIP) is described. A small amount of MIP has been synthesized within the pores of commercial polyethylene (PE) frits and attached to its surface using benzophenone (BP), a photo-initiator capable to start the polymerisation from the surface of the support material. Key properties affecting the obtainment of a proper polymeric layer, such as polymerisation time and kind of cross-linker were optimised. The developed imprinted material has been applied as a selective sorbent for cleaning extracts of thiabendazole (TBZ), as model compound, from citrus samples. The use of different solvents for loading the analyte in the imprinted frits was investigated, as well as the binding capacity of the imprinted polymer. Imprinted frits showed good selectivity when loads were performed using toluene and a linear relationship was obtained for the target analyte up to 1000 ng of loaded analyte. Prepared composite material was applied to the SPE of TBZ in real samples extracts, showing an impressive clean-up ability. Calibrations showed good linearity in the concentration range of 0.05-5.00 μg g(-1), referred to the original solid sample, and the regression coefficients obtained were greater than 0.996. The calculated detection limit was 0.016 μg g(-1), low enough to satisfactory analysis of TBZ in real samples. RSDs at different spiking levels ranged below 15% in all the cases and imprinted frits were reusable without loss in their performance.     

Divergent synthetic approach to 6'-modified α-GalCer analogues

A synthetic approach is presented for the synthesis of galacturonic acid and D-fucosyl modified KRN7000. The approach allows for late-stage functionalisation of both the sugar 6'-OH and the sphingosine amino groups, which enables convenient synthesis of promising 6'-modified KRN7000 analogues.     

Backscattering interferometry: an alternative approach for the study of hydrogen bonding interactions in organic solvents

Intermolecular interactions involving hydrogen bonds are responsible for catalysis and recognition. Traditional methods used to study hydrogen-bonding interactions are generally limited to relatively large volumes and high substrate concentrations. Backscattering Interferometry (BSI) provides a microfluidic platform to study these interactions in nonaqueous media at micromolar to nanomolar concentrations in picoliter volumes by monitoring changes in the refractive index.     

Computational design of a β-peptide that targets transmembrane helices

The design of β-peptide foldamers targeting the transmembrane (TM) domains of complex natural membrane proteins has been a formidable challenge. A series of β-peptides was designed to stably insert in TM orientations in phospholipid bilayers. Their secondary structures and orientation in the phospholipid bilayer was characterized using biophysical methods. Computational methods were then devised to design a β-peptide that targeted a TM helix of the integrin α(IIb)β(3). The designed peptide (β-CHAMP) interacts with the isolated target TM domain of the protein and activates the intact integrin in vitro.     

Linear and nonlinear optical properties of cationic bipyridyl iridium(III) complexes: tunable and photoswitchable?

A series of cationic Ir(III) substituted bipyridyl ()(N(∧)N (N(∧)N-bpy) complexes incorporating electron-donor and -acceptor substituents, [Ir(C(∧)N-ppy-R')(2)(N(∧)N-bpy-CH═CH-C(6)H(4)-R)][X] (X(-) = PF(6)(-) or C(12)H(25)SO(3)(-)), 2 (a, R = NEt(2) and R' = Me; b, R = O-Oct and R' = Me; c, R = NO(2) and R' = C(6)H(13); C(∧)N-ppy = cyclometalated 2-phenylpyridine, [Ir(C(∧)N-ppy-Me)(2)(N(∧)N-bpy-CH═CH-thienyl-Me)][PF(6)], 2d, and the dithienylethene (DTE)-containing complex 2e have been synthesized and characterized, and their absorption, luminescence, and quadratic nonlinear optical (NLO) properties are reported. Density functional theory (DFT) and time-dependent-DFT (TD-DFT) calculations on the complexes facilitate a detailed assignment of the excited states involved in the absorption and emission processes. All five complexes are luminescent in a rigid glass at 77 K, displaying vibronically structured spectra with long lifetimes (14-90 μs), attributed to triplet states localized on the styryl-appended bipyridines. The second-order NLO properties of 2a-d and related complexes 1a-d with 1,10-phenanthrolines have been investigated by both electric field induced second harmonic generation (EFISH) and harmonic light scattering (HLS) techniques. They are characterized by high negative EFISH μβ values which decrease when the ion pair strength between the cation and the counterion (PF(6)(-), C(12)H(25)SO(3)(-)) increases. The EFISH response is mainly controlled by metal-to-ligand charge-transfer/ligand-to-ligand charge-transfer (MLCT/L'LCT) processes. A combination of HLS and EFISH techniques is used to evaluate both the dipolar and octupolar contributions to the total quadratic hyperpolarizability, demonstrating that the major contribution is controlled by the octupolar part. The incorporation of a photochromic DTE unit into the N(∧)N-bpy ligand (complex 2e) allows the luminescence to be switched ON or OFF. The photocyclisation of the DTE unit can be triggered by using either UV (365 nm) or visible light (430 nm), leading to an efficient quenching of the ligand-based 77 K luminescence, which can be restored upon irradiation of the closed form at 715 nm. In contrast, no significant modification of the EFISH μβ value is observed upon photocyclization, suggesting that the quadratic NLO response is dominated by the MLCT/L'LCT processes, rather than by the intraligand excited states localized on the substituted bipyridine ligand.