Incoherent quasielastic neutron scattering study of molecular dynamics of 4-n-octyl-4'-cyanobiphenyl

We report incoherent quasielastic neutron scattering experiments on the thermotropic liquid crystal 4-n-octyl-4'-cyanobiphenyl. The combination of time-of-flight and backscattering data allows analysis of the intermediate scattering function over about three decades of relaxation times. Translational diffusion and uniaxial molecular rotations are clearly identified as the major relaxation processes in, respectively, the nanosecond and picosecond time scales.     

Synthesis, structure and magnetic behavior of five-coordinate bis(iminopyrrolyl) complexes of cobalt(II) containing PMe3 and THF ligands

The new bis-iminopyrrolyl five-coordinate Co(II) complexes [Co(kappa (2) N, N'-NC 4H 3C(R)N-2,6- (i)Pr 2C 6H 3) 2(PMe 3)] (R = H 3a; Me 3b) were synthesized in high yields (ca. 80-90%), using THF and diethyl ether as solvents, respectively, by (a) treatment of CoCl 2(PMe 3) 2 with the corresponding iminopyrrolyl Na salts ( Ie or If) or (b) reaction of anhydrous CoCl 2 and PMe 3 with Ie or If. A third route was tested, involving the addition of excesses of PMe 3 to the complexes [Co(kappa (2) N, N'-NC 4H 3C(R)N-2,6- (i)Pr 2C 6H 3) 2] (R = H 1e; Me 1f), which was only successful for the synthesis of 3a, in lower yields (ca. 30%). The synthesis of 3b in THF was unfruitful because of the kinetic competition of the solvent, giving rise to mixtures of 1f and its coordinated THF adduct 4b. The synthesis of the new bis-iminopyrrolyl five-coordinate Co(II) complexes [Co(kappa (2) N, N'-NC 4H 3C(R)N-2,6- (i)Pr 2C 6H 3) 2(THF)] (R = H 4a; Me 4b) were carried out in high yields (ca. 80-90%) by the reaction of CoCl 2(THF) 1.5 with the corresponding iminopyrrolyl Na salt. All the compounds have been characterized by X-ray diffraction, with 3a and 3b showing axially compressed trigonal bipyramidal geometry (with the PMe 3 ligand lying on the equatorial plane), whereas complexes 4a and 4b exhibit distorted square pyramidal geometries with the THF molecule occupying the axial position. Complex 4a shows clearly a compressed geometry, but for complex 4b, two polymorphs were characterized, exhibiting molecules with different Co-O (THF) bond lengths, one of them being compatible with an elongated form. Magnetic measurements either in the solid or in the liquid phases indicate that complexes 3a and 3b have low-spin ground states ( S = 1/2). In toluene solution, the geometry is fully confirmed by EPR data, which further indicates a d x (2) - y (2) /d xy ground state. However, compounds 4a and 4b behave unusually because they show magnetic moments that are compatible with high-spin ground states ( S = 3/2) in the solid state, but conform to low-spin ground states ( S = 1/2) when both complexes are dissolved in toluene solutions. The low-spin ground states in toluene solution are confirmed by EPR spectroscopy, which further supports, for complexes 4a and 4b, an axially elongated square pyramidal geometry and a d z (2) ground state. Thus the change in the ground-state and, consequently, in the geometry of complexes 4a and 4b from solid state to toluene solution might be a consequence of the elongation of the Co-O(THF) bond length. DFT studies performed on complexes 3 and 4 corroborate their different structure and magnetic behaviors and verify, for the latter complexes, the structural differences observed in the solid state and in toluene solution.     

Multiplexing fibre optic near infrared (NIR) spectroscopy as an emerging technology to monitor industrial bioprocesses

The application of near infrared spectroscopy in bioprocessing has been limited by its dependence on calibrations derived from single bioreactor at a given time. Here, we propose a multiplexed calibration technique which allows calibrations to be built from multiple bioreactors run in parallel. This gives the flexibility to monitor multiple vessels and facilitates calibration model transfer between bioreactors. Models have been developed for the two key analytes: glucose and lactate using Chinese hamster ovary (CHO) cell lines and using analyte specific information obtained from the feasibility studies. We observe slight model degradation for the multiplexed models in comparison to the conventional (single probe) models, decrease in r² values from 89.4% to 88% for glucose whereas for lactate from 92% to 91.8% and a simultaneous increase in the number of factors as the model incorporates the inter-probe variability, nevertheless the models were fit for purpose. The results of this particular application of implementing multiplexed-NIRS to monitor multiple bioreactor vessels are very encouraging, as successful models have been built on-line and validated externally, which proffers the prospect of reducing timelines in monitoring the vessels considerably, and in turn, providing improved control.     

Biomolecule-nanoparticle hybrids as functional units for nanobiotechnology

Biomolecule-metal or semiconductor nanoparticle (NP) hybrid systems combine the recognition and catalytic properties of biomolecules with the unique electronic and optical properties of NPs. This enables the application of the hybrid systems in developing new electronic and optical biosensors, to synthesize nanowires and nanocircuits, and to fabricate new devices. Metal NPs are employed as nano-connectors that activate redox enzymes, and they act as electrical or optical labels for biorecognition events. Similarly, semiconductor NPs act as optical probes for biorecognition processes. Double-stranded DNA or protein chains that are modified with metallic nanoclusters act as templates for the synthesis of metallic nanowires. The nanowires are used as building blocks to assemble nano-devices such as a transistor or a nanotransporter.     

(NHC)AuI]-catalyzed formation of conjugated enones and enals: an experimental and computational study

The [(NHC)AuI]-catalyzed (NHC=N-heterocyclic carbene) formation of alpha,beta-unsaturated carbonyl compounds (enones and enals) from propargylic acetates is described. The reactions occur at 60 degrees C in 8 h in the presence of an equimolar mixture of [(NHC)AuCl] and AgSbF6 and produce conjugated enones and enals in high yields. Optimization studies revealed that the reaction is sensitive to the solvent, the NHC, and, to a lesser extent, to the silver salt employed, leading to the use of [(ItBu)AuCl]/AgSbF6 in THF as an efficient catalytic system. This transformation proved to have a broad scope, enabling the stereoselective formation of (E)-enones and -enals with great structural diversity. The effect of substitution at the propargylic and acetylenic positions has been investigated, as well as the effect of aryl substitution on the formation of cinnamyl ketones. The presence or absence of water in the reaction mixture was found to be crucial. From the same phenylpropargyl acetates, anhydrous conditions led to the formation of indene compounds via a tandem [3,3] sigmatropic rearrangement/intramolecular hydroarylation process, whereas simply adding water to the reaction mixture produced enone derivatives cleanly. Several mechanistic hypotheses, including the hydrolysis of an allenol ester intermediate and SN2' addition of water, were examined to gain an insight into this transformation. Mechanistic investigations and computational studies support [(NHC)AuOH], produced in situ from [(NHC)AuSbF6] and H2O, instead of cationic [(NHC)AuSbF6] as the catalytically active species. Based on DFT calculations performed at the B3LYP level of theory, a full catalytic cycle featuring an unprecedented transfer of the OH moiety bound to the gold center to the C[triple chemical bond]C bond leading to the formation of a gold-allenolate is proposed.     

Synthesis,Structural Characterization,and In Vitro and In Silico Antifungal Evaluation of Azo-Azomethine Pyrazoles (PhN2(PhOH)CHN(C3N2(CH3)3)PhR,R = H or NO2)

The azo-azomethine imines, R¹-N=N-R²-CH=N-R³, are a class of active pharmacological ligands that have been prominent antifungal, antibacterial, and antitumor agents. In this study, four new azo-azomethines, R¹ = Ph, R² = phenol, and R³ = pyrazol-Ph-R’ (R = H or NO₂), have been synthesized, structurally characterized using X-ray, IR, NMR and UV–Vis techniques, and their antifungal activity evaluated against certified strains of Candida albicans and Cryptococcus neoformans. The antifungal tests revealed a high to moderate inhibitory activity towards both strains, which is regulated as a function of both the presence and the location of the nitro group in the aromatic ring of the series. These biological assays were further complemented with molecular docking studies against three different molecular targets from each fungus strain. Molecular dynamics simulations and binding free energy calculations were performed on the two best molecular docking results for each fungus strain. Better affinity for active sites for nitro compounds at the “meta” and “para” positions was found, making them promising building blocks for the development of new Schiff bases with high antifungal activity.     

Multiphysics Simulation Combining Large-Eddy Simulation,Wall Heat Conduction and Radiative Energy Transfer to Predict Wall Temperature Induced by a Confined Premixed Swirling Flame

A multi-physics simulation combining large-eddy simulation, conjugate heat transfer and radiative heat transfer is used to predict the wall temperature field of a confined premixed swirling flame operating under atmospheric pressure. The combustion model accounts for the effect of enthalpy defect on the flame structure whose stabilization is here sensitive to the wall heat losses. The conjugate heat transfer is accounted for by solving the heat conduction within the combustor walls and with the Hybrid-Cell Neumann-Dirichlet coupling method, enabling to dynamically adapt the coupling period. The latter coupling procedure is enhanced to determine statistics (mean, RMS, \(\ldots \)) in a permanent regime accurately and efficiently thanks to an acceleration technique which is derived and validated. The exact radiative heat transfer equation is solved with an advanced Monte Carlo method with a local control of the statistical error. The coupled simulation is carried out with or without accounting for radiation. Excellent results for the wall temperature are achieved by the fully coupled simulation which are then further analyzed in terms of radiative effects, global energy budget and fluctuations of wall heat flux and temperature.     

Application and Modification of Cyclometalated Ruthenium(II) Complex [Ru(o-C6H4-2-C5H4N)- (MeCN)4]PF6 for Atom Transfer Radical Polymerization

Polymerizations of n-butyl acrylate (BA), methyl methacrylate (MMA) and styrene (St) were promoted by the Ru(II) cyclometalated complex with labile MeCN ligand in the presence of Al(OiPr)₃. The polymerization proceeds via radical mechanism and requires the loss of MeCN ligand. The poor control over the polymerizations can be explained in terms of the traditional ATRP scheme. However, the controllability may be significantly improved by addition of reducing SnCl₂. Mechanism of the process is proposed.