The sign of the lithium—carbon nuclear spin coupling constant in methyllithium tetramer

Heteronuclear magnetic double resonance experiments are used to show that ¹J(⁷Li—¹³C) is positive in methyllithium tetramer. This is consistent with dominance of the coupling mechanism by the Fermi contact interaction.     

Nano-structured calcium silicate hydrate functionalised with iodine

Nano-structured calcium silicate hydrate can physisorb or chemisorb iodine, making it interesting for medical or materials science applications, where a slow, controlled release of iodine is desired. It was found that iodine can be sorbed and released by applying the elemental halogen in solution, either as a gas or as a solid. At ambient temperatures the sorption and desorption process is quantitative and physical, meaning that the same amount of iodine is taken up and released. At temperatures above 32.5 °C (305.7 K) iodine reacts with the calcium silicate hydrate forming a complex, which is stable above the sublimation temperature of iodine. The formation energy for the iodine calcium silicate hydrate complex was established to be 41.8 ± 0.8 kJ mol⁻¹ by calorimetry and the nature of the complex was investigated using X-ray photoelectron spectroscopy.     

Retrieval of aerosol optical depth in vicinity of broken clouds from reflectance ratios: Sensitivity study

We conducted a sensitivity study to better understand the potential of a new method for retrieving aerosol optical depth (AOD) under partly cloudy conditions. This method exploits ratios of reflectances in the visible spectral range and provides an effective way to avoid three-dimensional (3D) cloud effects. The sensitivity study is performed for different observational conditions and random errors in input data. The results of the sensitivity study suggest that this ratio method has the ability to detect clear pixels even in close proximity to clouds. Such detection does not require a statistical analysis of the two-dimensional (2D) horizontal distribution of reflected solar radiation, which makes it suitable for operational retrievals. In comparison with previously suggested approaches, the ratio method has the capability to increase the “harvest” of clear pixels. Similar to the traditional independent pixel approximation (IPA), the ratio method has a low computational cost for retrieving AOD. In contrast to the IPA method, the ratio method provides much more accurate estimations of the AOD values under broken cloud conditions: pixel-based and domain-averaged estimations of errors in AOD are about 25% and 10%, respectively. Finally, both the ratio-based cloud screening and the accuracy of domain-averaged ratio-based AOD values do not suffer greatly when 5% random errors are introduced in the reflectances.     

Graphical Sensitivity Analysis for Multidimensional Scaling

This article introduces graphical sensitivity analysis for multidimensional scaling. This new technique is designed to combat two problems associated with multidimensional scaling analyses: The possibility of local minima and the uncertainty regarding sensitivity of the solution to changes in the parameters. Graphical sensitivity analysis is currently available in ViSta-MDS, a test bed for graphical model examination. By graphically manipulating points in the solution space, analysts may examine the sensitivity of the solution to changes in the model parameters. Furthermore, the analyst may search for alternative solutions that represent local minima. An example of graphical sensitivity analysis using ViSta-MDS is described.     

A critical view of the yawn-sigh as a voice therapy technique

The purpose of this study was to take a critical look at a voice therapy technique known as the yawn-sigh. The voiced sigh as an approach in voice therapy has had increased use in recent years, particularly with problems of vocal hyperfunction. In this study, the physiology of the yawn-sigh was studied with video nasoendoscopy in eight normal subjects; their taped voices were also studied acoustically for possible fundamental frequency and formant changes in producing selected vowels under normal and sigh conditions. Although each subject was given a model by the examiner of a yawn-sigh, one of the eight subjects could not produce a true yawn-sigh. Endoscopic findings for seven of the eight subjects performing the yawn-sigh demonstrated retracted elevation of the tongue, a lower positioning of the larynx, and a widened pharynx. Acoustic analyses for the seven subjects producing the sigh found a marked lowering of the second and third formants. Implications for using the yawn-sigh in voice therapy are given, such as using a modified “silent” yawn-sigh, as an easy method for producing greater vocal tract relaxation.     

A viologen-based UV indicator and dosimeter

A UV indicator/dosimeter based on benzyl viologen (BV²⁺) encapsulated in polyvinyl alcohol (PVA) is described. Upon exposure to UV light, the BV²⁺/PVA film turns a striking purple colour due to the formation of the cation radical, BV^•+. The usual oxygen sensitivity of BV^•+ is significantly reduced due to the very low oxygen permeability of the encapsulating polymer, PVA. Exposure of a typical BV²⁺/PVA film, for a set amount of time, to UVB light with different UV indices produces different levels of BV^•+, as measured by the absorbance of the film at 550 nm. A plot of the change in absorbance at this wavelength, ΔAbs(550), as a function of UV index, UVI, produces a linear calibration curve which allows the film to be used as a UVB indicator, and a similar procedure could be employed to allow it to be used as a solar UVI indicator. A typical BV²⁺/PVA film generates a significant, semi-permanent (stable for >24 h) saturated purple colour (absorbance ~0.8–0.9) upon exposure to sunlight equivalent to a minimal erythemal dose associated with Caucasian skin, i.e. skin type II. The current drawbacks of the film and the possible future use of the BV²⁺/PVA film as a personal solar UV dosimeter for all skin types are briefly discussed.      

Comparative performance of CF3I,CD3I and CH3I in an atomic iodine photodissociation laser

We have compared the performance of CF₃I, CD₃I, and CH₃I in an atomic iodine photodissociation laser over the pressure range 1–200 torr. At pressures below 5 torr, CD₃I produces larger energy outputs, while above 5 torr CF₃I gives superior performance. The crossing of the laser energy output versus pressure curves is explained on the basis of collisional quenching of I(²P_{$\text{1}\text{2}$})(≡I^*) by undissociated alkyl iodide.     

Synthesis and reactivity of the methoxozirconium pentatungstate (nBu4N)6[{(mu-MeO)ZrW5O18}2]: insights into proton-transfer reactions, solution dynamics, and assembly of {ZrW5O18}2- building blocks

The methoxo-bridged, dimeric, ZrIV-substituted Lindqvist-type polyoxometalate (POM) (nBu4N)6[{(mu-MeO)ZrW5O18}2], (TBA)61, has been synthesized by stoichiometric hydrolysis of Zr(OnPr)4, [{Zr(OiPr)3(mu-OnPr)(iPrOH)}2], or [{Zr(OiPr)4(iPrOH)}2] and [{WO(OMe)4}2] in the presence of (nBu4N)2WO4, providing access to the systematic nonaqueous chemistry of ZrW5 POMs for the first time and an efficient route to 17O-enriched samples for 17O NMR studies. 1H NMR provided no evidence for dissociation of 1 in solution, although exchange with MeOH was shown to be slow by an EXSY study. Reactions with HX at elevated temperatures gave a range of anions [{XZrW5O18}n]3n- (X = OH, 3; OPh, 4; OC6H4Me-4, 5; OC6H4(CHO)-2, 6; acac, 7; OAc, 8), where n = 2 for 3 and n = 1 for 4-8, while 1H and 17O NMR studies of hydrolysis of 1 revealed the formation of an intermediate [(mu-MeO)(mu-HO)(ZrW5O18)2]6-. Electrospray ionization mass spectrometry of 1 and 3 illustrated the robust nature of the ZrW5O18 framework, and X-ray crystal structure determinations showed that steric interactions between ligands X and the ZrW5O18 surface are important. The coordination number of Zr is restricted to six in aryloxides 4 and 5, while seven-coordination is achieved in the chelate complexes 6-8. Given the inert nature of the methoxo bridges in 1, protonation of ZrOW sites is proposed as a possible step in reactions with HX. The diphenylphosphinate ligand in [(Ph2PO2)ZrW5O18]3- was found to be labile and upon attempted recrystallization the aggregate [(mu3-HO)2(ZrW5O18)3H]7- 9 was formed, which was found to be protonated at ZrOZr and ZrOW sites. This work demonstrates the flexibility of the {ZrW5O18}2- core as a molecular platform for modeling catalysis by tungstated zirconia surfaces.