Dark uncertainty

Standard uncertainties obtained by the GUM approach for a range of analytical methods are compared directly and indirectly with estimates of reproducibility standard deviation for the same methods. Results were obtained from both routine analysis and international key comparisons. A general tendency for the uncertainty to be substantially less than the reproducibility standard deviation was found.     

Meltblown fibers: Influence of viscosity and elasticity on diameter distribution

Both melt viscosity (η_o) and elasticity (correlated here with the longest melt relaxation time λ₁) were found to control the diameter distribution of meltblown fibers. Fibers were formed by melt blowing binary polystyrene (PS) blends containing widely differing component molecular weights using a custom-built laboratory apparatus. Varying the concentration and molecular weight of a high molecular weight PS provided independent control over η_o and λ₁. These rheological parameters influence the average diameter (d_av) and the distribution of diameters (coefficient of variation, CV) of meltblown fibers in different ways. Increasing η_o leads to an increase in d_av but has little impact on CV. On the other hand, increasing λ₁ beyond a threshold value reduces CV while simultaneously increasing d_av. A one-dimensional slender-jet theoretical model with both upper convected Maxwell and Phan–Thien and Tanner constitutive equations was developed to investigate the influence of viscoelasticity and processing parameters on the properties of meltblown fibers. This model predicts a strong dependence of fiber diameter on the air shear stress and variations in fiber diameter with viscoelasticity that are in qualitative agreement with the experimental results. We believe these results suggest that carefully controlling the viscoelastic profile of polymers used in melt blowing is a viable approach for producing nanofibers with narrow fiber diameter distributions using current commercial equipment.     

Kripke submodels and universal sentences

We define two notions for intuitionistic predicate logic: that of a submodel of a Kripke model, and that of a universal sentence. We then prove a corresponding preservation theorem. If a Kripke model is viewed as a functor from a small category to the category of all classical models with (homo)morphisms between them, then we define a submodel of a Kripke model to be a restriction of the original Kripke model to a subcategory of its domain, where every node in the subcategory is mapped to a classical submodel of the corresponding classical model in the range of the original Kripke model. We call a sentence universal if it is built inductively from atoms (including ? and ⊥) using ∧, ∨, ?, and →, with the restriction that antecedents of → must be atomic. We prove that an intuitionistic theory is axiomatized by universal sentences if and only if it is preserved under Kripke submodels. We also prove the following analogue of a classical model‐consistency theorem: The universal fragment of a theory Γ is contained in the universal fragment of a theory Δ if and only if every rooted Kripke model of Δ is strongly equivalent to a submodel of a rooted Kripke model of Γ. Our notions of Kripke submodel and universal sentence are natural in the sense that in the presence of the rule of excluded middle, they collapse to the classical notions of submodel and universal sentence. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Method validation in analytical sciences: discussions on current practice and future challenges

Accreditation and Quality Assurance - Eurachem held a workshop on method validation in analytical sciences in Gent, Belgium, on 9–10 May 2016. A summary of the working group discussions is...     

Polymeric cross-linked surface treatments for controlling block copolymer orientation in thin films

The orientation of cylinder-forming poly(styrene-block-methyl methacrylate) [P(S-b-MMA)] was investigated on two sets of polymeric surface treatments: 10 para-substituted polystyrene derivatives with <10 mol % poly(4-vinylbenzyl azide) and a series of poly(styrene-random-4-vinylbenzyl azide) [P(S-r-VBzAz)] copolymers with 5-100 mol % poly(4-vinylbenzyl azide). The copolymers were spin-coated to form thin films and then cross-linked by heating. The resulting films exhibited a range of surface tensions from 21 to 45 dyn/cm. Perpendicular orientation of P(S-b-MMA) cylinders was achieved with poly(p-bromostyrene) and all the [P(S-r-VBzAz)] copolymer surface treatments, most notably the homopolymer of poly(4-vinylbenzyl azide). Films made from these simple copolymers are as effective as random terpolymer alignment layers commonly made from both block monomers and a cross-linkable monomer.     

Immobilized boron-centered heteroscorpionates: heterocycle metathesis and coordination chemistry

The preparation of a resin-supported boron-scorpionate ligand and its nickel(II) coordination complexes are reported. The supported ligand is prepared as its potassium salt, making it a general reagent suitable for chelation of any transition metal ion. Resin-immobilized benzotriazole (Bead-btz) reacted cleanly with KTp* (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) by heterocycle metathesis in warm dimethylformamide (DMF) to yield bead-Tp'K, {resin-btz(H)B(pz*)(2)}K. Significantly, bead-Tp'K readily bound nickel(II) from simple salts with minimal leaching of the nickel ion. Bead-Tp'NiNO(3) reacts further with cysteine thiolate (ethyl ester), imparting the deep green color to the beads characteristic of a Tp(R)NiCysEt coordination sphere. Bead-Tp'NiCysEt exhibited an oxygen sensitivity similar to Tp*NiCysEt in solution (Inorg. Chem. 1999, p 5690) and also independently verified for a selenocystamine analogue, Tp*NiSeCysAm. Addition of fresh cysteine thiolate ethyl ester to oxidized bead-Tp'NiCysEt reproduced the original green color. Heterocycle metathesis was also used to prepare KTp' as a white solid. Reaction with nickel(II) gave (Tp')(2)Ni, separable into two different isomers. The air-sensitive molybdenum(0) complex, [PPh(4)][Tp'Mo(CO)(3)], was also prepared and the C(s) complex symmetry demonstrated by infrared and (13)C NMR spectroscopies. Immobilized TpmMo(CO)(3) was prepared from the previously reported resin-supported tris(pyrazolyl)methane. In contrast to its weak coordination of nickel(II) (Inorg. Chem. 2009, p 3535), bead-Tpm proved a strong chelate toward this second row metal. The supported scorpionates described here should find use in studies of selective metal-protein binding, metalloprotein modeling, and heterogeneous catalysis, and render such scorpionate applications amenable to combinatorial methods.     

Solvation of amino acid residues in water and urea-water mixtures: Volumes and heat capacities of 20 amino acids in water and in 8 molar urea at 25°C

The limiting partial molar volumes V ^o and heat capacities C _p ^o of 20 amino acids have been determined in water and in 8 molar urea at 25.0°C using flow calorimetry and flow densimetry. The side chain contributions to V ^o and C _p ^o were obtained as the difference between the properties of the various amino acids and those of glycine, both in water and in 8M urea. The solvent accessible surface area of the amino acid residues were obtained using a method developed by Hermann, and the total surface areas were separated into their hydrophobic A _Hb and hydrophilic components. In water, C _p ^o values for the various residues C _p ^o (R) were found well correlated with A _Hb , though much less so in the urea solution. Hence, C _p ^o (R) values, in water yield a good estimate of side chain hydrophobicity, but the (waterurea) transfer heat capacities appear strongly affected by specific solvation effects in the urea solution.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.     

Osteryoung square-wave voltammetric determination of nicarbazin in chicken tissue

Osteryoung square-wave voltammetric analysis is a rapid technique that can be used to determine nicarbazin residues in chicken tissue. The method is reproducible and can be applied to samples containing as little as 1-10 mug/g nicarbazin. This level of sensitivity is more than adequate for meeting governmental regulations. Osteryoung square-wave voltammetry is significantly faster than classical differential pulse polarography.     

On the general band shape of photodetachment spectra of trapped electrons

Photodetachment cross sections of trapped electrons are expressed analytically by a one-parameter model with an initial 1s bound state and a final plane-wave state. The theoretical cross-section curve, location of the peak maximum, and band width are discussed. Calculated photoabsorption profiles compare fairly well with experimental data. Comment is made concerning the ω^?8/3 photon-energy dependence for the bound-continuum band shape previously proposed in resolution of the absorption spectrum of trapped electrons into bound-bound and bound-continuum bands.     

A high-resolution high-speed data acquisition system based on an IBM-PC 486, for control of a Fourier transform spectrometer

The mini-computer and control electronics of a Bruker 113v Fourier Transform Spectrometer (FTS), capable of 0.03 cm^–1 resolution for frequencies up to 4000cm^–1, have been replaced by an inexpensive IBM-PC 486-based system. The original performance is exceeded. JCAMP-DX standard is used for data exchange. The system can be adapted to any FTS or similar instrument which requires time domain data acquisition.