Experimental characterization and micromechanical modeling of superelastic response of a porous NiTi shape-memory alloy

Porous shape-memory alloys are usually brittle due to the presence of various nickel-titanium intermetallic compounds that are produced in the course of most commonly used synthesizing techniques. We consider here a porous NiTi shape-memory alloy (SMA), synthesized by spark-plasma sintering, that is ductile and displays full shape-memory effects over the entire appropriate range of strains. The porosity however is only 12% but the basic synthesizing technique has potential for producing shape-memory alloys with greater porosity that still are expected to display superelasticity and shape-memory effects. The current material has been characterized experimentally using quasi-static and dynamic tests at various initial temperatures, mostly within the superelastic strain range, but also into the plastic deformation regime of the stress-induced martensite phase. To obtain a relatively constant strain rate in the high strain-rate tests, a novel pulse-shaping technique is introduced. The results of the quasi-static experiments are compared with the predictions by a model that can be used to calculate the stress-strain response of porous NiTi shape-memory alloys during the austenite-to-martensite and reverse phase transformations in uniaxial quasi-static loading and unloading at constant temperatures. In the austenite-to-martensite transformation, the porous shape-memory alloy is modeled as a three-phase composite with the parent phase (austenite) as the matrix and the product phase (martensite) and the voids as the embedded inclusions, reversing the roles of austenite and martensite during the reverse transformation from fully martensite to fully austenite phase. The criterion of the stress-induced martensitic transformation and its reversal is based on equilibrium thermodynamics, balancing the thermodynamic driving force for the phase transformation, associated with the reduction of Gibbs’ free energy, with the resistive force corresponding to the required energy to create new interface surfaces and to overcome the energy barriers posed by various microstructural obstacles. The change in Gibbs’ free energy that produces the driving thermodynamic force for phase transformation is assumed to be due to the reduction of mechanical potential energy corresponding to the applied stress, and the reduction of the chemical energy corresponding to the imposed temperature. The energy required to overcome the resistance imposed by various nano- and subnano-scale defects and like barriers, is modeled empirically, involving three constitutive constants that are then fixed based on the experimental data. Reasonably good correlation is obtained between the experimental and model predictions.     

Screening for oxidative damage by engineered nanomaterials: a comparative evaluation of FRAS and DCFH

Several acellular assays are routinely used to measure oxidative stress elicited by engineered nanomaterials (ENMs), yet little comparative evaluations of such methods exist. This study compares for the first time the performance of the dichlorofluorescein (DCFH) assay which measures reactive oxygen species (ROS) generation, to that of the ferric-reducing ability of serum (FRAS) assay, which measures biological oxidant damage in serum. A diverse set of 28 commercially important and extensively characterized ENMs were tested on both the assays. Intracellular oxidative stress was also assessed on a representative subset of seven ENMs in THP-1 (phorbol 12-myristate 13-acetate matured human monocytes) cells. Associations between assay responses and ENM physicochemical properties were assessed via correlation and regression analysis. DCFH correlated strongly with FRAS after dose normalization for mass (R ² = 0.78) and surface area (R ² = 0.68). Only 10/28 ENMs were positive in DCFH versus 21/28 in FRAS. Both assays were strongly associated with specific surface area and transition metal content. Qualitatively, a similar response ranking was observed for acellular FRAS and intracellular reduced:oxidized glutathione ratio (GSH:GSSG) in cells. Quantitatively, weak correlation was found between intracellular GSSG and FRAS or DCFH (R ² < 0.25) even after calculating effective dose to cells. The FRAS assay was more sensitive than DCFH, especially for ENMs with low to moderate oxidative damage potential, and may serve as a more biologically relevant substitute for acellular ROS measurements of ENMs. Further in vitro and in vivo validations of FRAS against other toxicological endpoints with larger datasets are recommended.     

The bromination of triethylamine

The products of bromination of triethylamine have been reinvestigated and shown to be N.N-diethyl di- and tribromoacetamides. The rotational barrier for the dibromoamide was measured, E_a = 40 kJ mol^?1 and found to be considerably lower than that of N,N-diethylacetamide.     

Cucurbit[n]uril formation proceeds by step-growth cyclo-oligomerization

In contrast to the high yield formation of cucurbit[n]uril (CB[n]) from a 1:2 ratio of glycoluril to formaldehyde, the condensation of glycoluril with less than 2 equiv of formaldehyde delivers a reaction mixture that contains glycoluril oligomers (2-6) and CB[n] compounds that lack one or more methylene bridges known as nor-seco-cucurbit[n]urils (ns-CB[n]). In this paper we report the chromatographic purification of C-shaped glycoluril oligomers (dimer-hexamer), their characterization in solution, and their X-ray crystal structures. Quite interestingly, despite being acyclic glycoluril pentamer 5 and hexamer 6 retain the ability to bind to guests typical of CB[6] but are also able to expand their cavity to accommodate larger guests like cationic adamantane derivatives. We performed product resubmission experiments with glycoluril oligomers 2-6 and found preferences for the formation of specific ring sizes during CB[n] formation. A comprehensive mechanistic scheme is proposed that accounts for the observed formation of 2-6 and ns-CB[n]. Overall, the experiments establish that a step-growth cyclo-oligomerization process operates during CB[n] formation.     

Potent and selective peptidyl boronic acid inhibitors of the serine protease prostate-specific antigen

Prostate cancer cells produce high (microgram to milligram/milliliter) levels of the serine protease Prostate-Specific Antigen (PSA). PSA is enzymatically active in the extracellular fluid surrounding prostate cancers but is found at 1,000- to 10,000-fold lower concentrations in the circulation, where it is inactivated due to binding to abundant serum protease inhibitors. The exclusive presence of high levels of active PSA within prostate cancer sites makes PSA an attractive candidate for targeted imaging and therapeutics. A synthetic approach based on a peptide substrate identified first peptide aldehyde and then boronic acid inhibitors of PSA. The best of these had the sequence Cbz-Ser-Ser-Lys-Leu-(boro)Leu, with a K_i for PSA of 65 nM. The inhibitor had a 60-fold higher K_i for chymotrypsin. A validated model of PSA's catalytic site confirmed the critical interactions between the inhibitor and residues within the PSA enzyme.