Synthesis and luminescence properties of new red-shifted absorption lanthanide(III) chelates suitable for peptide and protein labelling

The synthesis and photo-physical properties of an original bis-pyridinylpyrazine chromophore efficiently sensitising europium(III) and samarium(III) are described. The corresponding lanthanide(III) complexes display in aqueous solutions a maximum excitation wavelength which is significantly red-shifted compared to the usual terpyridine-based chelates, and a valuable luminescence brightness above 2,000 dm(3) mol(-1) cm(-1) at 345 nm was obtained with a europium(III) derivative. Further functionalisation with three different bioconjugatable handles was also investigated and their ability to efficiently label a model hexapeptide was evaluated and compared. Finally, the best bioconjugatable europium(III) chelate was used in representative labelling experiments involving monoclonal antibodies and the luminescence features of the corresponding bioconjugates remained satisfactory.     

Cupric superoxo-mediated intermolecular C-H activation chemistry

The new cupric superoxo complex [LCu(II)(O(2)(?-))](+), which possesses particularly strong O-O and Cu-O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH). Kinetic studies indicated a first-order dependence on both the Cu complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases.     

NH+-F hydrogen bonding in a fluorinated "proton sponge" derivative: integration of solution, solid-state, gas-phase, and computational studies

We report detailed studies on the characterization of an intramolecular NH-F hydrogen bond formed within a fluorinated "proton sponge" derivative. An ammonium ion, generated from 8-fluoro-N,N-dimethylnaphthalen-1-amine, serves as a charged hydrogen bond donor to a covalently bound fluorine appropriately positioned on the naphthalene skeleton. Potentiometric titrations of various N,N-dimethylnaphthalen-1-amines demonstrate a significant increase in basicity when hydrogen bonding is possible. X-ray crystallography reveals that NH-F hydrogen bonding in protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine is heavily influenced by ion pairing in the solid state; bifurcated and trifurcated hydrogen bonds are formed depending on the counterion utilized. Compelling evidence of hydrogen bonding in the 8-fluoro-N,N-dimethylnaphthyl-1-ammonium cation is provided by gas-phase cryogenic vibrational photodissociation spectroscopy. Solution-phase infrared spectroscopy provides complementary results, and the frequencies of the N-H stretching mode in both phases are in excellent agreement with the computed vibrational spectra. NMR analysis of protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine demonstrates significant H-F coupling between the N-H hydrogen and fluorine that cannot be attributed to long-range, through-bond interactions; the couplings correlate favorably with calculated values. The results obtained from these experiments are congruent with the formation of an NH-F hydrogen bond upon protonation of 8-fluoro-N,N-dimethylnaphthalen-1-amine.     

Rheo-attenuated total reflectance infrared spectroscopy: a new tool to study biopolymers

Whilst rheology is the reference technique to study the mechanical properties of unspun silk, we know little of the structure and the dynamics that generate them. By coupling infrared spectroscopy and shearing forces to study silk fibroin conversion, we are introducing a novel tool to address this gap in our knowledge. Here the silk conversion process has been studied dynamically using polarized attenuated total reflectance Fourier transform infrared spectroscopy whilst applying shear, thus revealing silk protein conformation and molecular orientation in situ. Our results show that the silk conversion process starts with a pre-alignment of the proteins followed by a rapid growth of the β-sheet formation and then a subsequent deceleration of the growth. We propose that this tool will provide further insight into not only silk but any biopolymer solution, opening a new window into biological materials.     

Carbon dioxide flow boiling in a single microchannel - Part I: Pressure drops

Carbon dioxide two-phase flow pressure drops have been investigated in a single horizontal stainless-steel micro-tube having a 0.529 mm inner diameter. Experiments were carried out in adiabatic conditions for four saturation temperatures of −10; −5; 0; 5 °C and mass fluxes ranging from 200 to 1400 kg/m² s, for inlet qualities up to unity. Measurements have been compared to the predictions of well-known methods. The Müller-Steinhagen and Heck correlation and the Friedel correlation gave the best fit as well as the homogeneous model when the liquid viscosity is used to represent the apparent two-phase viscosity. Further, an analysis based on the homogeneous model has not shown any clear appearance of the laminar or the transition regimes in any given range of Reynolds number. The apparent viscosity of the two-phase mixture was found larger than the liquid viscosity at low vapour qualities, namely at the lowest temperatures. Hence, a new expression to determine the equivalent viscosity was suggested as a function of the reduced pressure. Lastly, the Chisholm parameter from the Lockhart-Martinelli correlation was found lower than expected and also mainly dependent on the saturation temperature.     

Optimized absorption imaging of mesoscopic atomic clouds

We report on the optimization of high-intensity absorption imaging for small Bose–Einstein condensates. The imaging calibration exploits the linear scaling of the quantum projection noise with the mean number of atoms for a coherent spin state. After optimization for atomic clouds containing up to 300 atoms, we find an atom number resolution of $\varDelta_{\rm det}= 3.7$ atoms, mainly limited by photon shot noise and radiation pressure.     

Laser-induced incandescence technique to identify soot nucleation and very small particles in low-pressure methane flames

This paper presents the study we carried out on the formation of soot particles in low-pressure premixed CH₄/O₂/N₂ flames by using Laser-Induced Incandescence (LII). Flames were stabilised at 26.6 kPa (200 torr). Four different equivalence ratios were tested (Φ = 1.95, 205, 2.15 and 2.32), Φ = 1.95 corresponding to the equivalence ratio for which LII signals begin to be measurable along the flame. The evolution of the LII signals with laser fluence (fluence curve), time (temporal decay) and emission wavelength is reported at different heights above the burner. We specifically took advantage of the low-pressure conditions to probe with a good spatial resolution the soot inception zone of the flames. Significant different behaviours of the fluence curves are observed according to the probed region of the flames and Φ. In addition, while the surface growth process is accompanied by an increase in the LII decay-times (indicator of the primary particle diameter) at higher Φ, decay-times become increasingly short at lower Φ reaching a constant value along the flame at Φ = 1.95. These behaviours are consistent with the detection of the smallest incandescent particles in the investigated flames, these particles having experienced very weak surface growth. Flame modelling including soot formation has been implemented in flames Φ = 2.05 and 2.32. Experimental quantitative soot volume fraction profiles were satisfactorily reproduced by adjusting the fraction of reactive soot surface available for reactions. The qualitative variation of the computed soot particle diameter and the relative weight of surface growth versus nucleation were consistent with the experimental observations.     

A framework for predicting gross institutional long-term care cost arising from known commitments at local authority level

As the UK population ages, it is forecasted that there will be an unsustainable increase in the need for, and therefore in the costs of long-term care. Although several studies have been performed to estimate these costs, they do not take into account the impact of survival patterns on costs. Focussing only on residents already in care (known commitments), we have developed, in association with an English local authority, a framework for estimating the future gross cost incurred by this group, built around a survival model. We apply this framework to forecast the cost over a given period of time, of maintaining a group of individuals in residential and nursing care, funded by the local authority. One of the novelties in the model is that it translates survival inputs and unit fees for care into cost in a manner, which was useful and meaningful to decision makers.     

Response of an alumina fiber-reinforced aluminum composite to combined tension torsion

Aluminum coupons reinforced undirectionally with continuous alumina fibers were loaded in combined tension-torsion. Experimental results indicate that the super-imposition of a 0.0025 shear strain reduced the tensile strain to failure by 67 percent. Similarly, the superposition of a 0.0007 tensile strain reduced the shear strain to failure by 81 percent. It was inferred that applying the torque first and then the axial load or the axial load first and then the torque, had no significant affect on the failure envelope. The shear modulus was estimated to be 50.56.GPa.