Temperature-dependent hydrogen-bond geometry in liquid water

We have determined the hydrogen-bond geometry in liquid water from 0 to 80 degrees C by combining measurements of the proton magnetic shielding tensor with ab initio density functional calculations. The resulting moments of the distributions of hydrogen-bond length and angle are direct measures of thermal disorder in the hydrogen-bond network. These moments, and the distribution functions that can be reconstructed from them, impose quantitative constraints on structural models of liquid water.     

Design of donor–acceptor–donor (D–A–D) type small molecule donor materials with efficient photovoltaic parameters

Four Donor–Acceptor–Donor (D–A–D) type of donor molecules (M1‐M4) with triphenylamine (TPA) as donor moiety, thiophene as bridge, and thiazolothiazole as acceptor unit were designed and its photovoltaic parameters were equated with reference molecule “R.” DFT functional CAM‐B3LYP/6‐31G (d,p) was found best for geometry optimization and TD‐CAM‐B3LYP/6‐31G (d,p) was found suitable for excited state calculations. Among designed donor molecules, M4 manifests suitable lowest band gap of 4.73 eV, frontier molecular orbital energy levels as well as distinctive broad absorption of 455.3 nm due to the stronger electron withdrawing group. The electron‐withdrawing substituents contribute to red shifts of absorption spectra and better stabilities for designed molecules. The theoretically determined reorganization energies of designed donor molecules suggested excellent charge mobility property. The lower λ_e values in comparison with λ_h illustrated that these four donor materials would be ideal for electron transfer and M4 would be best amongst the investigated molecules with lowest λ_e of 0.0177. Furthermore, the calculated Voc of M4 is 2.04 V with respect to PC₆₀BM (phenyl‐C61‐butyric acid methyl ester). This study revealed that the designed donor materials are suitable and recommended for high performance organic solar cell devices.     

Synthesis of a small library of non-symmetric cyclic sulfamide HIV-1 protease inhibitors

A set of 11 non-symmetric cyclic sulfamide HIV-1 protease inhibitors were synthesized and evaluated. The use of a key microwave-assisted silver(I) oxide mediated selective mono N-benzylation reaction enabled fast and straightforward synthesis. The K_i values of the new inhibitors ranged between 0.28 μM and >20 μM.     

Monitoring of troponin release from cardiomyocytes during exposure to toxic substances using surface plasmon resonance biosensing

Troponin T (TnT) is a useful biomarker for studying drug-induced toxicity effects on cardiac cells. We describe how a surface plasmon resonance (SPR) biosensor was applied to monitor the release of TnT from active HL-1 cardiomyocytes in vitro when exposed to cardiotoxic substances. Two monoclonal human TnT antibodies were compared in the SPR immunosensor to analyse the TnT release. The detection limit of TnT was determined to be 30 ng/ml in a direct assay set-up and to be 10 ng/ml in a sandwich assay format. Exposure of the cardiomyocytes to doxorubicin, troglitazone, quinidine and cobalt chloride for periods of 6 and 24 h gave significant SPR responses, whereas substances with low toxicity showed insignificant effects (ascorbic acid, methotrexate). The SPR results were verified with a validated immunochemiluminescence method which showed a correlation of r ² = 0.790.     

Dispersion properties of planar Bragg waveguides

We reformulate the leaky mode condition of planar Bragg waveguides as two simple, separate conditions on the propagation constant; a phase match condition and a loss formula. These relations enable efficient numerical calculations of the mode properties. Furthermore, we use the phase match condition as a starting point to discuss the dispersion of waveguides with advanced cladding structures. In particular, we point out that chirped claddings, where the effective reflection point is dependent on frequency, do not give dispersion characteristics significantly different from metallic waveguides or waveguides with periodic claddings.     

Hertz contact at finite friction and arbitrary profiles

Axisymmetric contact at finite Coulomb friction and arbitrary profiles is examined analytically and numerically for dissimilar linear elastic solids. Invariance and generality are aimed at and an incremental procedure is developed resulting in a reduced benchmark problem corresponding to a rigid flat indentation of an elastic half-space. The reduced problem, being independent of loading and contact region, was solved by a finite element method based on a stationary contact contour and characterized by high accuracy. Subsequently, a tailored cumulative superposition procedure was developed to resolve the original problem to determine global and local field values. Save for the influence of the coefficients of friction and contraction ratio, it is shown that at partial slip the evolving relative stick-slip contour is independent of any convex and smooth contact profile at monotonic loading. For flat and conical profiles with rounded edges and apices, results are illustrated for relations between force, depth and contact contours together with surface stress distributions. The solution for dissimilar solids in a full space is transformed to a half-space problem and solved for a combination of material parameters in order to first determine interface traction distributions. Subsequently, full field values for the two solids were computed individually. In order to predict initiation of fracture and plastic flow, results are reported for the location and magnitude of maximum tensile stress and effective stress, respectively, for a range of geometrical and material parameters. In two illustrations, predicted results are compared with experimental findings related to initiation of brittle fracture and load-depth relations at nanoindentation.     

Method validation in analytical sciences: discussions on current practice and future challenges

Accreditation and Quality Assurance - Eurachem held a workshop on method validation in analytical sciences in Gent, Belgium, on 9–10 May 2016. A summary of the working group discussions is...     

Hertzian fracture at unloading

Hertzian fracture through indentation of flat float glass specimens by steel balls has been examined experimentally. Initiation of cone cracks has been observed and failure loads together with contact and fracture radii determined at monotonically increasing load but also during unloading phases. Contact of dissimilar elastic solids under decreasing load may cause crack inception triggered by finite interface friction and accordingly the coefficient of friction was determined by two different methods. In order to make relevant predictions of experimental findings, a robust computational procedure has been developed to determine global and local field values in particular at unloading at finite friction. It was found that at continued loading it is possible to specify in advance how the contact domain divides into invariant regions of stick and slip. The maximum tensile stress was found to occur at the free surface just outside the contact contour, the relative distance depending on the different elastic compliance properties and the coefficient of friction. In contrast, at unloading invariance properties are lost and stick/slip regions proved to be severely history dependant and in particular with an opposed frictional shear stress at the contact boundary region. This causes an increase of the maximum tensile stress at the contour under progressive unloading. Predictions of loads to cause crack initiation during full cycles were made based on a critical stress fracture criterion and proved to be favourable as compared to the experimental results.     

Nuclear spin quenching A new probe of exchange kinetics and droplet size in disperse systems

A new experimental technique, nuclear spin quenching (NSQ), is introduced, which can be used to measure droplet size and inter-droplet exchange rates of various intrinsic molecular species in disperse systems. The physical basis of the method is the quenching of the fine structure in spin-coupled N.M.R. spectra by intermolecular proton exchange, the rate of which is controlled by droplet exchange. The theoretical framework needed to interpret NSQ experiments is presented as well as an experimental case study on a water-in-oil microemulsion system. Being non-perturbing and having a large dynamic range, the NSQ technique should become a valuable complement to existing techniques for the study of structure and dynamics in disperse fluids.