The microwave spectrum and centrifugal distortion constants of propiolic acid

The microwave spectra of propiolic acid and propiolic acid-d have been measured up to J = 30. These have enabled accurate evaluation of the rotational and centrifugal distortion constants for each species. The measured frequencies are presented, along with some predictions of transitions unmeasured in the present work, but of potential use in radioastronomy.     

Anti-Substitution Intuitions and the Content of Belief Reports

Philosophers of language traditionally take it that anti-substitution intuitions teach us about the content of belief reports. Jennifer Saul [1997, 2002 (with David Braun), 2007] challenges this lesson. Here I offer a response to Saul’s challenge. In the first two sections of the article, I present a common sense justification for drawing conclusions about content from anti-substitution intuitions. Then, in Sect. 3, I outline Saul’s challenge—what she calls ‘the Enlightenment Problem’. Finally, in Sect. 4, I argue that Saul’s challenge does not undermine the common sense justification presented in Sects. 1 and 2. I avoid the challenge by arguing that anti-substitution intuitions are not directly sensitive to the content of the sentences that produce them, but rather to the possibility that one could have distinct ways of thinking about an object.     

Interplay of structure and reactivity in a most unusual furan Diels-Alder reaction

Difluorinated alkenoate ethyl 3,3-difluoro-2-(N,N-diethylcarbamoyloxy)-2-propenoate reacts rapidly and in high yield with furan and a range of substituted furans in the presence of a tin(IV) catalyst. Non-fluorinated congener 2-(N,N-diethylcarbamoyloxy)-2-propenoate fails to react at all under the same conditions. These reactions have been explored using density functional theory (DFT) calculations. They reveal a highly polar transition state, which is stabilized by the Lewis acid catalyst SnCl(4) and by polar solvents. In the presence of both catalyst and solvent, a two-step reaction is predicted, corresponding to the stepwise formation of the two new carbon-carbon bonds via transition states which have similar energies in all cases. Our experimental observations of the lack of reaction of the non-fluorinated dienophile, the stereochemical outcomes, and the rate acceleration accompanying furan methylation are all well predicted by our calculations. The calculated free energy barriers generally correlate well with measured reaction rates, supporting a reaction mechanism in which zwitterionic character is developed strongly. An in situ ring opening reaction of exo-cycloadduct ethyl exo-2-(N,N-diethylcarbamoyloxy)-3,3-difluoro-7-oxabicyclo[2.2.1]hept-5-enyl-2-endo-carboxylate, which results in the formation of cyclic carbonate ethyl 4,4-difluoro-5-hydroxy-2-oxo-5,7a-dihydro-4H-benzo[1,3]dioxole-3a-carboxylate by a Curtin-Hammett mechanism, has also been examined. Substantial steric opposition to Lewis acid binding prevents carbonate formation from 2-substituted furans.     

Achieving traceable chemical measurements: inter-laboratory evaluation of a simplified technique for isotope dilution mass spectrometry (IDMS). Part 1: Methodology for high accuracy analysis of trace metals

A high accuracy measurement procedure developed and validated at the Laboratory of the Government Chemist (LGC) has been transferred to a number of expert United Kingdom laboratories and their experience in applying the technique has been evaluated by inter-laboratory comparisons. It is an approximate matching calibration procedure for analysis of trace metals using isotope dilution mass spectrometry (IDMS). Use of a calibration blend and a sample blend having closely matched isotope amount ratios reduces systematic errors. Four comparisons were carried out, each evaluating an increasingly difficult aspect of the methodology. The final study required determination of trace levels of cadmium in an artificial food matrix acid digest containing tin, using both external calibration and approximate matching IDMS. The results of the trials clearly showed the superior accuracy of the IDMS approximate matching procedure; a result within 1% of the target reference value could be achieved. These trials and a training workshop enabled LGC to transfer its methodology to other expert laboratories, helping to improve the United Kingdom delivery of traceable reference measurements.     

Fourier transform microwave spectroscopy of aluminum hydrosulfide, AlSH

Pure rotational transitions of three isotopic species of aluminum hydrosulfide, AlSH, have been measured with a cavity pulsed jet Fourier transform microwave spectrometer. AlSH was prepared by the reaction of laser ablated Al metal with H₂S, and was stabilized in pulsed supersonic free jets of Ar. For each species the transition 1₀₁-0₀₀ was measured; hyperfine structure due to the nuclear spin of ²⁷Al was observed for the first time and analyzed. For Al³²SH and Al³²SD, the rotational constants are in excellent agreement with published values. For the third species, Al³⁴SH, this is the first observation, and its rotational constants are consistent with the published geometry. Information on the electronic structure of the molecule has been obtained using the ²⁷Al nuclear quadrupole coupling constants and nuclear spin-rotation constants. The latter have been used to evaluate ²⁷Al NMR shielding parameters, which are compared with those of other ²⁷Al compounds. These shieldings have been found to be in excellent agreement with theoretical predictions. The results should also help facilitate astrophysical searches for the molecule.     

Microwave spectra of the ground vibrational state of formaldehyde substituted with 17O and 18O

Pure rotational transitions in the ground vibrational state have been measured for H₂¹²C¹⁸O, H₂¹²C¹⁷O, H₂¹³C¹⁸O, and H₂¹³C¹⁷O in the frequency region 8–75 GHz. These have included both Q- and R-branch transitions, and have permitted accurate evaluation of rotational constants and several quartic centrifugal distortion constants for each species. These in turn have permitted the prediction of several transitions of possible use in radioastronomy.