Tris-2-(3-methylindolyl)phosphine as an anion receptor

A C3-symmetric phosphine with indolyl substituents has been synthesized that demonstrates the capability to bind anions through the indole NH sites and coordinate metal centres through the phosphorus centre.     

Dynamics of dilute water in carbon tetrachloride

A dilute solution of water in a hydrophobic solvent, such as carbon tetrachloride (CCl4), presents an opportunity to study the rotational properties of water without the complicating effects of hydrogen bonds. We report here the results of theoretical, experimental, and semiempirical studies of a 0.03 mole percent solution of water in CCl4. It is shown that for this solution there are negligible water-water interactions or water-CCl4 interactions; theoretical and experimental values for proton NMR chemical shifts (deltaH) are used to confirm the minimal interactions between water and the CCl4. Calculated ab initio values and semiempirical values for oxygen-17 and deuterium quadrupole coupling constants (chi) of water/CCl4 clusters are reported. Experimental values for the 17O, 2H, and 1H NMR spin-lattice relaxation times, T1, of 0.03 mole percent water in dilute CCl4 solution at 291 K are 94+/-3 ms, 7.0+/-0.2 s, and 12.6+/-0.4 s, respectively. These T1 values for bulk water are also referenced. "Experimental" values for the quadrupole coupling constants and relaxation times are used to obtain accurate, experimental values for the rotational correlation times for two orthogonal vectors in the water molecule. The average correlation time, tauc, for the position vector of 17O (orthogonal to the plane of the molecule) in monomer water, H2(17)O, is 91 fs. The average value for the deuterium correlation time for the deuterium vector in 2H2O is 104 fs; this vector is along the OD bond. These values indicate that the motion of monomer water in CCl4 is anisotropic. At 291 K, the oxygen rotational correlation time in bulk 2H2(17)O is 2.4 ps, the deuterium rotational correlation time in the same molecule is 3.25 ps. (Ropp, J.; Lawrence, C.; Farrar, T. C.; Skinner, J. L. J. Am. Chem. Soc. 2001, 123, 8047.) These values are a factor of about 20 longer than the tauc value for dilute monomer water in CCl4.     

Imaging ion-molecule reactions: charge transfer and C-N bond formation in the C(+) + NH3 system

The velocity mapping ion imaging method is applied to the ion-molecule reactions occurring between C(+) and NH(3). The velocity space images are collected over the relative collision energy range from 1.5 to 3.3 eV, allowing both product kinetic energy distributions and angular distributions to be obtained from the data. The charge transfer process appears to be direct, dominated by long-range electron transfer that results in minimal deflection of the products. The product kinetic energy distributions are consistent with a process dominated by energy resonance. The kinetic energy distributions for C-N bond formation appear to scale with the total available energy, providing strong evidence that energy in the [CNH(3)](+) precursor to products is distributed statistically. The angular distributions for C-N bond formation show pronounced forward-backward symmetry, as expected for a complex that resembles a prolate symmetric top decaying along its symmetry axis.     

Experimental studies of using wireless energy transmission for powering embedded sensor nodes

A major challenge impeding the deployment of wireless sensor networks for structural health monitoring (SHM) is developing a means to supply power to the sensor nodes in an efficient manner. In this paper, we explore possible solutions to this challenge by using a mobile-host based wireless energy transmission system to provide both power and data interrogation commands to sensor nodes. The mobile host features the capability of wirelessly transmitting energy to sensor nodes on an as-needed basis. In addition, it serves as a central data repository and processing center for the data collected from the sensing network. The wirelessly transmitted microwave energy is captured by a receiving antenna, transformed into DC power by a rectifying circuit, and stored in a storage medium to provide the required energy to the sensor node. The application of wireless energy transmission is targeted toward SHM sensor nodes that have been recently developed by the authors, which can be used to collect peak mechanical displacements or piezoelectric impedance measurements. This paper will describe considerations needed to design such energy transmission systems, experimental procedure and results, method of increasing the efficiency, energy conditioning circuits and storage medium, and target applications. Experimental results from a field test on the Alamosa Canyon Bridge in southern New Mexico will also be presented.     

An experimental investigation of change detection in uncertain chain-like systems

Promising ongoing research on “smart” sensing technologies is offering low-cost alternatives and new opportunities for large-scale SHM. Networks of sensors with wireless communication and computational capabilities can be used to increase the spatial resolution of data collection while providing a distributed computing framework for implementing structural health monitoring algorithms. Robust and practical SHM methodologies being able to rapidly and accurately detect and assess changes in the monitored system are required to be at the core of these “smart” structures. A data-driven non-parametric identification technique is used to implement a robust change detection methodology for uncertain MDOF chain-like systems that can be implemented in densely distributed smart-sensor networks. Experimental data from a test-bed structure tested at Los Alamos National Laboratory are used to evaluate the effectiveness and reliability of the proposed SHM methodology. The results of this study showed that the proposed approach was able, in a rigorous statistical framework, to confidently detect the presence of structural changes, accurately locate the structural section where the change occurred, and provide an accurate estimate of the actual level of “change”. Additionally, a full-order finite element model of the test structure, as well as the results from the experimental modal identification using the ERA algorithm were employed to validate the results obtained in this change-detection study.     

Machine learning and semi-empirical calculations: a synergistic approach to rapid,accurate, and mechanism-based reaction barrier prediction

Modern QM modelling methods, such as DFT, have provided detailed mechanistic insights into countless reactions. However, their computational cost inhibits their ability to rapidly screen large numbers of substrates and catalysts in reaction discovery. For a C–C bond forming nitro-Michael addition, we introduce a synergistic semi-empirical quantum mechanical (SQM) and machine learning (ML) approach that allows the prediction of DFT-quality reaction barriers in minutes, even on a standard laptop using widely available modelling software. Mean absolute errors (MAEs) are obtained that are below the accepted chemical accuracy threshold of 1 kcal mol⁻¹ and substantially better than SQM methods without ML correction (5.71 kcal mol⁻¹). Predictive power is shown to hold when the ML models are applied to an unseen set of compounds from the toxicology literature. Mechanistic insight is also achieved via the generation of full SQM transition state (TS) structures which are found to be very good approximations for the DFT-level geometries, revealing important steric interactions in some TSs. This combination of speed, accuracy, and mechanistic insight is unprecedented; current ML barrier models compromise on at least one of these important criteria.

A synergistic approach that combines machine learning with semi-empirical methods enables the fast and accurate prediction of DFT-quality reaction barriers, with mechanistic insights available from semi-empirical transition state geometries.     

Trace-element analysis of argyle diamonds using instrumental neutron activation analysis

Thirty four elements were determined by instrumental neutron activation analysis in colourless, brown, and pink diamonds, with and without inclusions. These were compared with data obtained for similar elements in the host lamproite rock. The natural radioactivity of these samples was measured by instrumental techniques, and found to be negligible.     

Synthesis of polyfunctionalized biphenyls as intermediates for a new class of liquid crystals

A series of hexa- and octasubstituted biphenyls containing halogen, amino, nitro, and propylthio substituents were prepared by metal-mediated convergent synthesis from halobenzene precursors. The Pd-assisted C-C coupling methods were ineffective in the formation of the Ar-Ar bond except for the synthesis of 1b. All tetra-ortho-substituted biphenyls were prepared via Ullmann coupling reactions. The halogens were introduced after formation of the biphenyl by utilizing the directing properties of the amino group(s). In the case of 3b, a polyhalogenated benzene substrate was used for biphenyl formation via Ullmann coupling.