Syntheses,structure, and reactivity of acyclic enetriyne and enetetrayne derivatives

Sonogashira coupling of buta-1,3-diynylbenzene with ((2-iodophenyl)ethynyl)trimethylsilane and 1,2-diiodobenzene led to the novel enetriyne, 1-ethynyl-2-(phenylbuta-1,3-diynyl)benzene, and enetetrayne, 1,2-bis(phenylbuta-1,3-diynyl)benzene, respectively. Solid state structural and thermal analyses are also described. In solution, 1-ethynyl-2-(phenylbuta-1,3-diynyl)benzene was found to undergo thermal Bergman cyclization to afford 2-(phenylethynyl)naphthalene.     

Separation of cannabinoids on three different mixed‐mode columns containing carbon/nanodiamond/amine‐polymer superficially porous particles

Three mixed‐mode high‐performance liquid chromatography columns packed with superficially porous carbon/nanodiamond/amine‐polymer particles were used to separate mixtures of cannabinoids. Columns evaluated included: (i) reversed phase (C₁₈), weak anion exchange, 4.6 × 33 mm, 3.6 μm, and 4.6 × 100 mm, 3.6 μm, (ii) reversed phase, strong anion exchange (quaternary amine), 4.6×33 mm, 3.6 μm, and (iii) hydrophilic interaction liquid chromatography, 4.6 × 150 mm, 3.6 μm. Different selectivities were achieved under various mobile phase and stationary phase conditions. Efficiencies and peak capacities were as high as 54 000 N/m and 56, respectively. The reversed phase mixed‐mode column (C₁₈) retained tetrahydrocannabinolic acid strongly under acidic conditions and weakly under basic conditions. Tetrahydrocannabinolic acid was retained strongly on the reversed phase, strong anion exchange mixed‐mode column under basic polar organic mobile phase conditions. The hydrophilic interaction liquid chromatography column retained polar cannabinoids better than the (more) neutral ones under basic conditions. A longer reversed phase (C₁₈) mixed‐mode column (4.6 × 100 mm) showed better resolution for analytes (and a contaminant) than a shorter column. Fast separations were achieved in less than 5 min and sometimes 2 min. A real world sample (bubble hash extract) was also analyzed by gradient elution.     

Design,Synthesis, and Validation of a Novel [11C]Promethazine PET Probe for Imaging Abeta Using Autoradiography

Promethazine, an antihistamine drug used in the clinical treatment of nausea, has been demonstrated the ability to bind Abeta in a transgenic mouse model of Alzheimer’s disease. However, so far, all of the studies were performed in vitro using extracted tissues. In this work, we report the design and synthesis of a novel [¹¹C]promethazine PET radioligand for future in vivo studies. The [¹¹C]promethazine was isolated by RP-HPLC with radiochemical purity >95% and molar activity of 48 TBq/mmol. The specificity of the probe was demonstrated using human hippocampal tissues via autoradiography.     

Nonlinear phase field theory for fracture and twinning with analysis of simple shear

A phase field theory for coupled twinning and fracture in single crystal domains is developed. Distinct order parameters denote twinned and fractured domains, finite strains are addressed and elastic nonlinearity is included via a neo-Hookean strain energy potential. The governing equations and boundary conditions are derived; an incremental energy minimization approach is advocated for prediction of equilibrium microstructural morphologies under quasi-static loading protocols. Aspects of the theory are analysed in detail for a material element undergoing simple shear deformation. Exact analytical and/or one-dimensional numerical solutions are obtained in dimensionless form for stress states, stability criteria and order parameter profiles at localized fractures or twinning zones. For sufficient applied strain, the relative likelihood of localized twinning vs. localized fracture is found to depend only on the ratio of twin boundary surface energy to fracture surface energy. Predicted criteria for shear stress-driven fracture or twinning are often found to be in closer agreement with test data for several types of real crystals than those based on the concept of theoretical strength.     

Permeability anisotropy due to consolidation of compressible porous media

The characterisation of flow through porous media is important for all solid–liquid separation and fluid transport realms. The permeability of porous media can be anisotropic and furthermore, the extent of anisotropy can be increased as a result of an applied compressive force. However, the understanding of how anisotropy develops is incomplete. An overview of research on permeability anisotropy is given and an expression for predicting anisotropy as a function of void ratio is offered. The two underlying assumptions of the proposed model are: flow in different directions occurs within the same network of pores and deformation is primarily due to the compression of the particles in the direction of the applied force rather than due to particle rearrangement. The assumption of network connectivity allows permeability anisotropy to be described as a function of flow path tortuosity only. Results are presented for hydraulic anisotropy measured in lignite that has been upgraded by a compression dewatering method known as mechanical thermal expression. The lignite permeability is shown to be up to eight times greater in the direction perpendicular to compression, suggesting that the rate of dewatering could be significantly increased by choosing the drainage to also be perpendicular to the direction of the applied compressive force. It is illustrated that the proposed anisotropy model can be used to accurately predict the experimentally determined permeability anisotropy ratios for lignite, as well as for other materials including sand, clay and kaolin.     

Anholonomic configuration spaces and metric tensors in finite elastoplasticity

Deformation mappings are considered that correspond to the motions of lattice defects, elastic stretch and rotation of the lattice, and initial defect distributions. Intermediate (i.e., relaxed) configuration spaces associated with these deformation maps are identified and then classified from the differential-geometric point of view. A fundamental issue is the proper selection of coordinate systems and metric tensors in these configurations when such configurations are classified as anholonomic. The particular choice of a global, external Cartesian coordinate system and corresponding covariant identity tensor as a metric on an intermediate configuration space is shown to be a constitutive assumption often made regardless of the existence of geometrically necessary crystal defects associated with the anholonomicity (i.e., the non-Euclidean nature) of the space. Since the metric tensor on the anholonomic configuration emerges necessarily in the definitions of scalar products, certain transpose maps, tensorial symmetry operations, and Jacobian invariants, its selection should not be trivialized. Several alternative (i.e., non-Euclidean) representations proposed in the literature for the metric tensor on anholonomic spaces are critically examined.     

Studies of Mental “Noise”

Successive tests of subjects' performance in reaction time tasks were treated as time series and submitted to spectrum analysis. Rather than revealing the white noise expected by the view that variability is due to random error (equivalent power across frequency), the power spectra revealed colored noise. The slopes of the power spectra did not vary much for tasks differing in memory requirements. Spectrum analysis of time series from the logistic map also showed colored noise in regions on the edge of chaos, showing that the presence of colored noise in cognitive data need not oblige a theoretical account based on a complex, high-dimensional, system.     

Continuum modeling of twinning,amorphization, and fracture: theory and numerical simulations

A continuum mechanical theory is used to model physical mechanisms of twinning, solid-solid phase transformations, and failure by cavitation and shear fracture. Such a sequence of mechanisms has been observed in atomic simulations and/or experiments on the ceramic boron carbide. In the present modeling approach, geometric quantities such as the metric tensor and connection coefficients can depend on one or more director vectors, also called internal state vectors. After development of the general nonlinear theory, a first problem class considers simple shear deformation of a single crystal of this material. For homogeneous fields or stress-free states, algebraic systems or ordinary differential equations are obtained that can be solved by numerical iteration. Results are in general agreement with atomic simulation, without introduction of fitted parameters. The second class of problems addresses the more complex mechanics of heterogeneous deformation and stress states involved in deformation and failure of polycrystals. Finite element calculations, in which individual grains in a three-dimensional polycrystal are fully resolved, invoke a partially linearized version of the theory. Results provide new insight into effects of crystal morphology, activity or inactivity of different inelasticity mechanisms, and imposed deformation histories on strength and failure of the aggregate under compression and shear. The importance of incorporation of inelastic shear deformation in realistic models of amorphization of boron carbide is noted, as is a greater reduction in overall strength of polycrystals containing one or a few dominant flaws rather than many diffusely distributed microcracks.