Heterogeneous Electrofreezing Triggered by CO2 on Pyroelectric Crystals: Qualitatively Different Icing on Hydrophilic and Hydrophobic Surfaces

By performing icing experiments on hydrophilic and hydrophobic surfaces of pyroelectric amino acids and on the x‐cut faces of LiTaO₃, we discovered that the effect of electrofreezing of super cooled water is triggered by ions of carbonic acid. During the cooling of the hydrophilic pyroelectric crystals, a continuous water layer is created between the charged hemihedral faces, as confirmed by impedance measurements. As a result, a current of carbonic acid ions, produced by dissolved environmental CO₂, flows through the wetted layer towards the hemihedral faces and elevates the icing temperature. This proposed mechanism is based on the following: (i) on hydrophilic surfaces, water with dissolved CO₂ (pH 4) freezes at higher temperatures than pure water of pH 7. (ii) In the absence of the ionic current, achieved by linking the two hemihedral faces of hydrophilic crystals by a conductive paint, water of the two pH levels freeze at the same temperature. (iii) On hydrophobic crystals with similar pyroelectric coefficients, where there is no continuous wetted layer, no electrofreezing effect is observed.     

Synthesis and Mechanical Properties of sub 5-μm PolyUiO-66 Thin Films on Gold Surfaces

Metal-organic framework (MOF) thin films currently lack the mechanical stability needed for electronic device applications. Polymer-based metal-organic frameworks (polyMOFs) have been suggested to provide mechanical advantages over MOFs, however, the mechanical properties of polyMOFs have not yet been characterized. In this work, we developed a method to synthesize continuous sub-5 μm polyUiO-66(Zr) films on Au substrates, which allowed us to undertake initial mechanical property investigations. Comparisons between polyUiO-66 and UiO-66 thin films determined polyUiO-66 thin films exhibit a lower modulus but similar hardness to UiO-66 thin films. The initial mechanical characterization indicates that further development is needed to leverage the mechanical property advantages of polyMOFs over MOFs. Additionally, the demonstration in this work of a continuous surface-supported polyUiO-66 thin film enables utilization of this emerging class of polyMOF materials in sensors and devices applications.     

IUPAC critical evaluation of the rotational-vibrational spectra of water vapor. Part II: Energy levels and transition wavenumbers for HDO, HDO, and HDO

This is the second of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This article presents energy levels and line positions of the following singly deuterated isotopologues of water: HD¹⁶O, HD¹⁷O, and HD¹⁸O. The MARVEL (measured active rotational-vibrational energy levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0-22 708, 0-1674, and 0-12 105 cm⁻¹ for HD¹⁶O, HD¹⁷O, and HD¹⁸O, respectively. For HD¹⁶O, 54 740 transitions were analyzed from 76 sources, the lines come from spectra recorded both at room temperature and from hot samples. These lines correspond to 36 690 distinct assignments and 8818 energy levels. For HD¹⁷O, only 485 transitions could be analyzed from three sources; the lines correspond to 162 MARVEL energy levels. For HD¹⁸O, 8729 transitions were analyzed from 11 sources and these lines correspond to 1864 energy levels. The energy levels are checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators. This comparison shows that the measured transitions account for about 86% of the anticipated absorbance of HD¹⁶O at 296 K and that the transitions predicted by the MARVEL energy levels account for essentially all the remaining absorbance. The extensive list of MARVEL lines and levels obtained are given in the Supplementary Material of this article, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. In addition, the transition and energy level information for H₂¹⁷O and H₂¹⁸O, given in the first paper of this series [Tennyson, et al. J Quant Spectr Rad Transfer 2009;110:573-96], has been updated.     

Interactions between pairs of antimalarial drugs studied by experimental and ab initio (13)C NMR chemical shifts

The interactions between the antimalarial drugs chloroquine (CQ) and amodiaquine (AQ), chloroquine and quinine (QN), and amodiaquine and quinine are studied by (13)C NMR. Experimental changes in chemical shift are compared to nucleus-independent chemical shifts to determine the best structure of the complex formed by each drug pair in solution. Structures of the CQ-AQ and CQ-QN complexes are found to be similar to those found previously for the drug dimers. On the other hand, the best solution structure for the AQ-QN complex suggests that the quinoline rings of the two drugs are at an angle with respect to each other.     

Determination of chlorpyrifos and its metabolites in rat brain tissue using coupled-column liquid chromatography/electrospray ionization tandem mass spectrometry

A method has been developed to quantify chlorpyrifos (O,O-diethyl-O-[3,5,6,-trichloro-2-pyridyl] phosphorothionate) and its metabolites chlorpyrifos-oxon (O,O-diethyl-O-[3,5,6,trichloro-2-pyridinyl] phosphate) and TCP (3,5,6,-trichloro-2-pyridinol) in rat brain tissue by coupled-column liquid chromatography/electrospray ionization tandem mass spectrometry (LC/LC/ESI-MS/MS). Rat brains were homogenized and treated by protein precipitation using ice-cold acetonitrile. The supernatant was directly injected onto the coupled-column system. Sample clean-up was achieved on a Zorbax Extend-C(18) column (2.1 x 50 mm, 5 microm) using a mobile phase of acetonitrile/water with 0.0025% formic acid (40:60, v/v). The compounds were separated isocratically on a Zorbax Eclipse XDB C(8) column (2.0 x 150 mm, 5 microm) using a mobile phase of acetonitrile/water with 0.0025% formic acid (75:25, v/v). Chlorpyrifos and chlorpyrifos-oxon were detected in positive ion mode using multiple reaction monitoring (MRM). TCP was detected in negative ion mode using precursor-to-precursor transition monitoring. The method was validated and the specificity, linearity, limit of quantitation (LOQ), precision, accuracy, stability, and recoveries were determined. Calibration curves for all three analytes yielded correlation coefficients of 0.993 or greater. The LOQs were 25.3 ng/g for chlorpyrifos and 6.3 ng/g for chlorpyrifos-oxon and TCP. All precision relative standard deviations (RSDs) were less than 16% for the LOQ and less than 11% for the other QC samples. This method was successfully applied to six rats that were injected subcutaneously with chlorpyrifos.     

Determination of biogenic amines in wines by ion-pair liquid chromatography and post-column derivatization with 1,2-naphthoquinone-4-sulphonate

A liquid chromatographic method with post-column derivatization for the determination of biogenic amines in wines is proposed. The method is based on the separation of amines by ion-pair chromatography using sodium heptanesulfonate (SHS) and on-line labeling of analytes with 1,2-naphthoquinone-4-sulfonate. The principal factors influencing the separation (acetonitrile and SHS concentration) have been considered for the optimization of the elution gradient through factorial design and multicriteria decision-making. Figures of merit have been established using red wine samples. Detection limits range from 0.2 to 3 mg L(-1), the peak area run-to-run repeatability from 1.6 to 4.6% and the retention time repeatability lower than 1.2%. Recoveries ranging from 92 and 108% prove the accuracy of the method for determining ethanolamine, ethylamine, histamine and tyramine in commercial red wines. The proposed method has been applied to the analysis of wines from different Spanish regions.     

The irreducible characters of the alternating Hecke algebras

This paper computes the irreducible characters of the alternating Hecke algebras, which are deformations of the group algebras of the alternating groups. More precisely, we compute the values of the irreducible characters of the semisimple alternating Hecke algebras on a set of elements indexed by minimal length conjugacy class representatives and we show that these character values determine the irreducible characters completely. As an application, we determine a splitting field for the alternating Hecke algebras in the semisimple case.     

Some new Kirkman signal sets

A decomposition of the blocks of an \(\textsf {STS}(v)\) into partial parallel classes of size m is equivalent to a Kirkman signal set \(\textsf {KSS}(v,m)\). We give decompositions of \(\textsf {STS}(4v-3)\) into classes of size \(v-1\) when \(v \equiv 3 \pmod {6}\), \(v \not = 3\). We also give decompositions of \(\textsf {STS}(v)\) into classes of various sizes when v is a product of two arbitrary integers that are both congruent to \(3 \pmod {6}\). These results produce new families of \(\textsf {KSS}(v,m)\).