Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.     

An Ion-Exchangeable MOF with Reversible Dehydration and Dynamic Structural Behavior (NH4)2[Zn2(O3PCH2CH2COO)2]⋅5 H2O (BIRM-1)

(NH₄)₂[Zn₂(O₃PCH₂CH₂COO)₂]⋅5 H₂O (BIRM-1) is a new metal phosphonate material, synthesized through a simple hydrothermal reaction between zinc nitrate and 3-phosphonopropionic acid, using urea and tetraethylammonium bromide as the reaction medium. In common with other metal–organic framework materials, BIRM-1 has a large three-dimensional porous structure providing potential access to a high internal surface area. Unlike most others, it has the advantage of containing ammonium cations within the pores and has the ability to undergo cation exchange. Additionally, BIRM-1 also exhibits a reversible dehydration behavior involving an amorphization-recrystallization cycle. The ability to undergo ion exchange and dynamic structural behavior are of interest in their own right, but also increase the range of potential applications for this material. Here the crystal structure of this new metal phosphonate and its ion exchange behavior with K⁺ as an exemplar are studied in detail, and its unusual structure-reviving property reported.     

Antimicrobial Metabolites against Methicillin-Resistant Staphylococcus aureus from the Endophytic Fungus Neofusicoccum australe

Antimicrobial bioassay-guided fractionation of the endophytic fungi Neofusicoccum australe led to the isolation of a new unsymmetrical naphthoquinone dimer, neofusnaphthoquinone B (1), along with four known natural products (2–5). Structure elucidation was conducted by nuclear magnetic resonance (NMR) spectroscopic methods, and the antimicrobial activity of all the natural products was investigated, revealing 1 to be moderately active towards methicillin-resistant Staphylococcus aureus (MRSA) with a minimum inhibitory concentration (MIC) of 16 µg/mL.     

Roadside Drug Testing Approaches

The purpose of this review is to present an overview of roadside drug testing, driving enforcement, and drunk/drug driving detection around the world. Drunk and drug driving is a severe problem, not only in the UAE, but also around the world. This has important implications for road safety as drunk or drug driving may increase the chances of a driver’s involvement in a road crash when compared to a drug-free driver. Recently, due to increases in drug-impaired drivers’ crash involvement, many mobile roadside drug testing devices have been introduced to the market. These devices use oral fluid, urine or blood matrices. These are on-the-spot tests, which are easy to use and are applied by law enforcement agencies and the public. Law enforcement agencies most commonly use oral fluid to detect the presence of illicit drugs in drivers. This review discusses all the available devices in the market used by the authorities. It also describes the type of drugs widely abused by drivers along with behavioral testing methods. The different types of matrices used for roadside drug testing are also evaluated. Sample collection, storage, and pre-treatment methods are discussed, followed by the confirmatory analysis of positive samples. This article will significantly help law enforcement agencies compare and evaluate all the reliable roadside testing devices and new emerging confirmatory devices available to them in the market. This will help them make an informed decision on which device to adapt to their individual needs.     

Temperature profiles in a controlled-stress parallel plate rheometer

Actual melt temperatures are rarely measured directly when conducting rheological characterisations of materials in non-ambient conditions despite the potentially large influence temperature may have on the rheological data. For rheometers that use only a temperature-regulated lower plate, it is likely that the set point and true melt temperatures differ, an effect that becomes significant when characterising melts or suspensions close to phase-change events like crystallisation. This work investigates the magnitude of these effects for a controlled-stress rheometer featuring a temperature-controlled lower plate. The lower plate was fitted with a serrated cover disc that was found to exacerbate temperature deviations from the desired set point. Steady-state radial and vertical temperature profiles within the sample were measured and compared with the predictions of a finite element analysis model. The deviations between set point and measured temperatures were successfully predicted by the simulation for two typical gap heights for a thermoplastic, ceramic paste. The non-ideal heat transfer characteristics were also investigated numerically for a representative polymer system that demonstrated the increased deviations from ideal values for lower thermal conductivity materials.

Three-dimensional speckle interferometric investigation of the stress-intensity factor along a crack front

The variation in Mode I stress-intensity factor throughout the thickness of an ASTM standard compact tension specimen was determined using scattered-light speckle interferometry. Two very thin sheets of coincident coherent light traveling in opposite directions were passed through a Plexiglas specimen normal to the crack faces. A double-exposed photograph of the scattered-light speckle pattern was taken while the specimen was subjected to a small load increment. From this double-exposed photograph, the change in the crack-opening displacement could be determined. From the information about the crack-opening displacement in the region of the crack tip, the stress-intensity factor was calculated for various interior planes and on the surface of the specimen. For the compact tension specimen tested, the stress-intensity factor did not vary throughout the specimen's thickness. The method of scattered-light speckle interferometry proved to be very powerful in solving this complex three-dimensional problem.     

Dynamic measurements of initiation toughness at high loading rates

An experimental method is described for measuring the dynamic initiation toughness of a sharp stationary crack. A plane specimen is utilized which consists of a central region 50-mm wide and 200-mm long with integral dog-bone ends. The loading is accomplished by the detonation of four small explosive charges which produce two tensile stress waves upon reflection from the dog-bone ends. The stress waves meet at the midpoint of the specimen and reinforce to produce a relatively large, uniformly stressed region with a very high loading rate. The crack is positioned at the midpoint of the specimen at the location where the reinforcing tensile stress waves meet. A series of photoelastic experiments were conducted using Homalite 100 as the model material to observe, in a full-field view, the arrival of the dilatational waves, the subsequent development of the stress field at the tip of the stationary crack and the initiation of the crack. The isochromatic fringe pattern was also used to determine the instantaneous value of the stress-intensity factorK(t) after the characteristic fringe loops developed in the region near the crack tip. Finally,K(t) was measured using a single strain gage positioned and oriented so that its signal output was proportional toK(t) and independent of the next two higher order terms in the series representation of the strain field. A method was developed to determine the instant of initiation from the strain-time trace. Results obtained from the photoelastic and strain measurements of the dynamic-initiation toughnessK _ID were consistently higher than the static value ofK _IC . Paper was presented at the 1987 SEM Fall Conference on Experimental Mechanics held in Savannah, GA on October 25–28.     

Further studies on dynamic crack branching

The newly derived dynamic-crack-branching criterion with its modifications is verified by the dynamicphotoelastic results of dynamic crack branchings in thinpolycarbonate, single-edged crack-tension specimens. Successful crack branching was observed in four specimens and unsuccessful branching in another. Crack branching consistently occurred when the necessary conditions ofK _I =K _{I b} =3.3 MPa \(\sqrt m\) and the sufficiency condition ofr _o =r _c =0.75 mm were satisfied simultaneously. In the unsuccessful branching test, the necessary condition was not satisfied sinceK _I was always less thanK _{I b} .     

Investigation of the structure of detonation waves in a non-premixed hydrogen–air rotating detonation engine using mid-infrared imaging

The structure of detonation waves propagating through the annular channel of an optically accessible non-premixed rotating detonation engine (RDE) are investigated using mid-infrared imaging. The RDE is operated on hydrogen–air mixtures for a range of air mass flow rates and equivalence ratios. Instantaneous images of the radiation intensity from water vapor are acquired using a mid-infrared camera and a band-pass filter (2.890?±?0.033?µm). The instantaneous mid-infrared images reveal the stochastic nature of the detonation wave structure, position and angle of oblique and reflected shock waves, presence of shear layer separating products from the previous and current cycles, and extent of mixing between the reactants and products in the reactant fill zone in front of the detonation wave. The images show negligible signal directly in front of the detonation waves suggesting that there is minimal mixing between the reactants and products from the previous cycle ahead of the detonation wave for most operating conditions. The mid-infrared images provide insights useful for improving fundamental understanding of the detonation structure in RDEs and benchmark data for evaluating modeling and simulation results of RDEs.     

Beyond microstructures: Using the Kerr Effect to characterize the macrostructures of synthetic polymers

The macrostructures of synthetic polymers are essentially the complete molecular chain architectures, including the types and amounts of constituent short‐range microstructures, such as the regio‐ and stereosequences of the inserted monomers, the amounts and sequences of monomers found in co‐, ter‐, and tetra‐polymers, branching, inadvertent, and otherwise, etc. Currently, the best method for characterizing polymer microstructures uses high field, high resolution ¹³C‐nuclear magnetic resonance (NMR) spectroscopy observed in solution. However, even ¹³C‐NMR is incapable of determining the locations or positions of resident polymer microstructures, which are required to elucidate their complete macrostructures. The sequences of amino acid residues in proteins, or their primary structures, cannot be characterized by NMR or other short‐range spectroscopic methods, but only by decoding the DNA used in their syntheses or, if available, X‐ray analysis of their single crystals. Similarly, there are currently no experimental means to determine the sequences or locations of constituent microstructures along the chains of synthetic macromolecules. Thus, we are presently unable to determine their macrostructures. As protein tertiary and quaternary structures and their resulting ultimate functions are determined by their primary sequence of amino acids, so too are the behaviors and properties of synthetic polymers critically dependent on their macrostructures. We seek to raise the consciousness of both synthetic and physical polymer scientists and engineers to the importance of characterizing polymer macrostructures when attempting to develop structure–property relations. To help achieve this task, we suggest using the electrical birefringence or Kerr effects observed in their dilute solutions. The molar Kerr constants of polymer solutes contributing to the birefringence of their solutions, under the application of a strong electric field, are highly sensitive to both the types and locations of their constituent microstructures. As a consequence, we may begin to characterize the macrostructures of synthetic polymers by means of the Kerr effect. To simplify implementation of the Kerr effect to characterize polymer macrostructures, we suggest that NMR first be used to determine the types and amounts of constituent microstructures present. Subsequent comparison of observed Kerr effects with those predicted for different microstructural locations along the polymer chains can then be used to identify the most likely macrostructures. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 155–166