Harmonization and transferability of performance assessment: experience from four serum aluminum proficiency testing schemes

Proficiency testing schemes monitor laboratory performance and provide a stimulus for improvement in accuracy. Where several schemes operate in the same analytical sector, there are risks that assessments of performance may be in conflict. Performance assessment for the determination of trace elements such as aluminum in serum is particularly important due to the high risk of contamination and therefore erroneous results. The objectives of this work were (1) to compare several mathematical models to establish a predefined standard deviation for proficiency assessment and (2) to evaluate the influence of instrumental methods and proficiency testing scheme on the assessment of performance for serum aluminum measurements. For this purpose, three samples were sent to the participants of four proficiency testing schemes. Assigned values were calculated according to algorithm A according to ISO 13528 and standard deviation for proficiency assessment according to three methods based on individual variability, state of the art or previous proficiency testing results. The method based on individual variability produced a more stringent standard deviation compared to analytical imprecision based on the state of the art. The instrumental methods gave similar results, whereas significant differences were observed between the four proficiency testing schemes indicating that harmonization of the standard deviation for proficiency assessment fails to allow transferability from one proficiency testing scheme to another and that additional factor(s) contribute to variability in performance assessment.     

The MTE continuum relation with application to an argon arc at atmospheric pressure

The continuum emission coefficient relation for a plasma in Multithermal Equilibrium (MTE) is derived using the partial-MTE ionization equation. The results are presented in a form using the nonhydrogenic free-bound Gaunt factors of Schlüter. Measurements on a 200 A, 1 atm, constricted argon arc indicate that electron densities calculated from the MTE continuum relation and Schlüter's ξ_fb values exceed electron densities from the Stark broadening of H_β by 15–30%. Experimental values of ξ_fb are up to 3 times larger than Schlüter's values, but are in agreement with the values of Morris and Krey at 5 atm, which is probably one of the few similar experiments actually in or near complete LTE. In the present experiment at the arc axis: N_e(H_β) = 1.00 × 10¹⁷cm^-3 (±8%); T_e = 34,000 K (±20%); T_exa = 12,000 K (±3%); T_exβ = 9000 K (±5%); and T_a = T_i = 10,000 K (±68%). The probable errors reflect the need for more accurate transition probabilities which had an uncertainty of 25%.     

Downstream Conditions in a Constricted ARC with Radial Injection

The thermal, flow and electrical conditions are presented for the downstream portion of an argon arc with local fluid constriction. The arc is initially wall-stabilized in a 10 mm diameter water-cooled constrictor and at some point after flow becomes fully developed the arc is constricted by a radial inward jet. The redevelopment of the flow downstream of the injection slot is investigated by measurements of the pressure drop, wall heat flux and electric field. It is observed that redevelopment proceeds roughly as predicted by classical theory. Measurements of the electric field indicate that the region of maximum constriction is limited in extent.     

Parametric resonance and Hopf bifurcation analysis for a MEMS resonator

We study the response of a MEMS resonator, driven in an in-plane length-extensional mode of excitation. It is observed that the amplitude of the resulting vibration has an upper bound, i.e., the response shows saturation. We present a model for this phenomenon, incorporating interaction with a bending mode. We show that this model accurately describes the observed phenomena. The in-plane (“trivial”) mode is shown to be stable up to a critical value of the amplitude of the excitation. At this value, a new “bending” branch of solutions bifurcates. For appropriate values of the parameters, a subsequent Hopf bifurcation causes a beating phenomenon, in accordance with experimental observations.     

Caterpillar Track Complexes in Template‐Directed Synthesis and Correlated Molecular Motion

Small alterations to the structure of a star‐shaped template totally change its mode of operation. The hexapyridyl template directs the conversion of a porphyrin dimer to the cyclic hexamer, but deleting one pyridine site changes the product to the cyclic decamer, while deleting two binding sites changes the product to the cyclic octamer. This surprising switch in selectivity is explained by the formation of 2:1 caterpillar track complexes, in which two template wheels bind inside the nanoring. Caterpillar track complexes can also be prepared by binding the hexapyridyl template inside the 8‐ and 10‐porphyrin nanorings. NMR exchange spectroscopy (EXSY) experiments show that these complexes exhibit correlated motion, in which the conrotatory rotation of the two template wheels is coupled to rotation of the nanoring track. In the case of the 10‐porphyrin system, the correlated motion can be locked by binding palladium(II) dichloride between the two templates.     

Analysis of the surface-probe equation

An integrating surface-probe is a tool for the determination of local fluxes from surface-integrated measurements. For an axisymmetric system, the data analysis involves the numerical solution of a severely ill-conditioned Volterra integral equation of the first kind. This study establishes the existence of a unique solution under certain conditions and considers solution techniques based on product integration and also evaluation of the inversion integral. The methods are tested for convergence against exact input data, and the performance of the best methods against simulated experimental data is studied.     

Strengthening the security of authenticated key exchange against bad randomness

Recent history has revealed that many random number generators (RNGs) used in cryptographic algorithms and protocols were not providing appropriate randomness, either by accident or on purpose. Subsequently, researchers have proposed new algorithms and protocols that are less dependent on the RNG. One exception is that all prominent authenticated key exchange (AKE) protocols are insecure given bad randomness, even when using good long-term keying material. We analyse the security of AKE protocols in the presence of adversaries that can perform attacks based on chosen randomness, i.e., attacks in which the adversary controls the randomness used in protocol sessions. We propose novel stateful protocols, which modify memory shared among a user’s sessions, and show in what sense they are secure against this worst case randomness failure. We develop a stronger security notion for AKE protocols that captures the security that we can achieve under such failures, and prove that our main protocol is correct in this model. Our protocols make substantially weaker assumptions on the RNG than existing protocols.