CO2 laser-induced decomposition of propan-2-ol,butan-2-ol,pentan-2-ol,pentan-3-ol,and hexan-2-ol

The pulsed CO₂ laser-induced decompositions of propan-2-ol, butan-2-ol, pentan-2-ol, pentan-3-ol, and hexan-2-ol in the gas phase have been investigated. Like ethanol which we examined previously [1] the absorption cross section of propan-2-ol for pulsed 9R14 radiation increases with pressure at low pressures, an effect attributed to rotational hole-filling. In contrast the absorption cross section of butan-2-ol (10R24) has only a small pressure dependence and those of pentan-2-ol (9R26), pentan-3-ol (10R14), and hexan-2-ol (9P20) show little or no variation with pressure in the range 0.1–5.0 torr. Decomposition products have been investigated at low pressure where the excitation of the alkanols was essentially collision free. The observed products for all the alkanols can be rationalized on the basis of primary dehydration and C? C fission channels, with minor contributions from other molecular eliminations. © 1994 John Wiley & Sons, Inc.     

End‐to‐End Distances in Four‐Junction Polymers

The various end‐to‐end distances of four‐junction polymers are investigated. The sizes of the different kinds of equal length branches and the backbone of two different polymers, with either nine or eleven branches, are estimated by means of both renormalization‐group and MC calculations. The comparisons of first‐order ε = 4 − d predictions with the MC results are satisfactory. The same trends are present in both techniques. The excluded‐volume interactions from additional branches further expand the various parts of the chains so that internal branches are larger than external ones. The branch ratios in the eleven‐branch case are expanded even more than the corresponding ratios of the nine‐branch polymer.

     

Pinning frequencies of the collective modes in alpha-uranium

Uranium is the only known element that features a charge-density wave (CDW) and superconductivity. We report a comparison of the specific heat of single-crystal and polycrystalline alpha-uranium. In the single crystal we find excess contributions to the heat capacity at 41 K, 38 K, and 23 K, with a Debye temperature ThetaD = 265 K. In the polycrystalline sample the heat capacity curve is thermally broadened (ThetaD = 184 K), but no excess heat capacity was observed. The excess heat capacity Cphi (taken as the difference between the single-crystal and polycrystal heat capacities) is well described in terms of collective-mode excitations above their respective pinning frequencies. This attribution is represented by a modified Debye spectrum with two cutoff frequencies, a pinning frequency V0 for the pinned CDW (due to grain boundaries in the polycrystal), and a normal Debye acoustic frequency occurring in the single crystal.     

Quantum-to-classical transition in cavity quantum electrodynamics

The quantum properties of electromagnetic, mechanical or other harmonic oscillators can be revealed by investigating their strong coherent coupling to a single quantum two level system in an approach known as cavity quantum electrodynamics (QED). At temperatures much lower than the characteristic energy level spacing the observation of vacuum Rabi oscillations or mode splittings with one or a few quanta asserts the quantum nature of the oscillator. Here, we study how the classical response of a cavity QED system emerges from the quantum one when its thermal occupation-or effective temperature-is raised gradually over 5 orders of magnitude. In this way we explore in detail the continuous quantum-to-classical crossover and demonstrate how to extract effective cavity field temperatures from both spectroscopic and time-resolved vacuum Rabi measurements.     

Structural and electronic properties of group III Rich In0.53Ga0.47As(001)

The structural and electronic properties of group III rich In_0.53Ga_0.47As(001) have been studied using scanning tunneling microscopy/spectroscopy (STM/STS). At room temperature (300 K), STM images show that the In_0.53Ga_0.47As(001)–(4 × 2) reconstruction is comprised of undimerized In/Ga atoms in the top layer. Quantitative comparison of the In_0.53Ga_0.47As(001)–(4 × 2) and InAs(001)–(4 × 2) shows the reconstructions are almost identical, but In_0.53Ga_0.47As(001)–(4 × 2) has at least a 4× higher surface defect density even on the best samples. At low temperature (77 K), STM images show that the most probable In_0.53Ga_0.47As(001) reconstruction is comprised of one In/Ga dimer and two undimerized In/Ga atoms in the top layer in a double (4 × 2) unit cell. Density functional theory (DFT) simulations at elevated temperature are consistent with the experimentally observed 300 K structure being a thermal superposition of three structures. DFT molecular dynamics (MD) show the row dimer formation and breaking is facilitated by the very large motions of tricoodinated row edge As atoms and z motion of In/Ga row atoms induced changes in As–In/Ga–As bond angles at elevated temperature. STS results show there is a surface dipole or the pinning states near the valence band (VB) for 300 K In_0.53Ga_0.47As(001)–(4 × 2) surface consistent with DFT calculations. DFT calculations of the band-decomposed charge density indicate that the strained unbuckled trough dimers being responsible for the surface pinning.     

An integrated mass spectrometry imaging and digital pathology workflow for objective detection of colorectal tumours by unique atomic signatures

Tumours are abnormal growths of cells that reproduce by redirecting essential nutrients and resources from surrounding tissue. Changes to cell metabolism that trigger the growth of tumours are reflected in subtle differences between the chemical composition of healthy and malignant cells. We used LA-ICP-MS imaging to investigate whether these chemical differences can be used to spatially identify tumours and support detection of primary colorectal tumours in anatomical pathology. First, we generated quantitative LA-ICP-MS images of three colorectal surgical resections with case-matched normal intestinal wall tissue and used this data in a Monte Carlo optimisation experiment to develop an algorithm that can classify pixels as tumour positive or negative. Blinded testing and interrogation of LA-ICP-MS images with micrographs of haematoxylin and eosin stained and Ki67 immunolabelled sections revealed Monte Carlo optimisation accurately identified primary tumour cells, as well as returning false positive pixels in areas of high cell proliferation. We analysed an additional 11 surgical resections of primary colorectal tumours and re-developed our image processing method to include a random forest regression machine learning model to correctly identify heterogenous tumours and exclude false positive pixels in images of non-malignant tissue. Our final model used over 1.6 billion calculations to correctly discern healthy cells from various types and stages of invasive colorectal tumours. The imaging mass spectrometry and data analysis methods described, developed in partnership with clinical cancer researchers, have the potential to further support cancer detection as part of a comprehensive digital pathology approach to cancer care through validation of a new chemical biomarker of tumour cells.

Digital pathology and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) imaging reveals a unique elemental signature of colorectal cancer.     

Hierarchical microstructure in structural phase transitions

We consider a model in the context of martensitic materials in which hierarchical twinning near the habit plane (austenite-martensite interface) is a new and crucial ingredient. The model includes (1) a triple-well potential in local deviatoric (rectangular) strain, (2) strain gradient terms up to second order in strain and fourth order in gradient, and (3) all symmetry allowed compositional fluctuation-induced strain gradient terms. The last term favors branching of domain walls which enables communication between macroscopic and microscopic regions essential for shape memory. Below the transition temperature (T₀) we obtain the conditions under which branching of twins is energetically favorable. Above T₀ a hierarchy of branched domain walls also stabilizes tweed formation (criss-cross patterns of twins). External stress or pressure modulates (“patterns”) the spacing of domain walls. Results based on 2D time-dependent Ginzburg-Landau simulations are shown for twins, tweed and hierarchy formation.     

Static search games played over graphs and general metric spaces

We define a general game which forms a basis for modelling situations of static search and concealment over regions with spatial structure. The game involves two players, the searching player and the concealing player, and is played over a metric space. Each player simultaneously chooses to deploy at a point in the space; the searching player receiving a payoff of 1 if his opponent lies within a predetermined radius r of his position, the concealing player receiving a payoff of 1 otherwise. The concepts of dominance and equivalence of strategies are examined in the context of this game, before focusing on the more specific case of the game played over a graph. Methods are presented to simplify the analysis of such games, both by means of the iterated elimination of dominated strategies and through consideration of automorphisms of the graph. Lower and upper bounds on the value of the game are presented and optimal mixed strategies are calculated for games played over a particular family of graphs.     

Simultaneous isolation and label‐free identification of bacteria using contactless dielectrophoresis and Raman spectroscopy

The traditional bacterial identification method of growing colonies on agar plates can take several days to weeks to complete depending on the growth rate of the bacteria. Successfully decreasing this analysis time requires cell isolation followed by identification. One way to decrease analysis time is by combining dielectrophoresis (DEP), a common technique used for cell sorting and isolation, and Raman spectroscopy for cell identification. DEP‐Raman devices have been used for bacterial analysis, however, these devices have a number of drawbacks including sample heating, cell‐to‐electrode proximity that limits throughput and separation efficiency, electrode fouling, or inability to address sample debris. Presented here is a contactless DEP‐Raman device to simultaneously isolate and identify particles from a mixed sample while avoiding common drawbacks associated with other DEP designs. Using the device, a mixed sample of bacteria and 3 μm polystyrene spheres were isolated from each other and a Raman spectrum of the trapped bacteria was acquired, indicating the potential for cDEP‐Raman devices to decrease the analysis time of bacteria.