Stacking Gaussian processes to improve $$pK_a$$ p K a predictions in the SAMPL7 challenge

Journal of Computer-Aided Molecular Design - Accurate predictions of acid dissociation constants are essential to rational molecular design in the pharmaceutical industry and elsewhere. There has...     

Teaching the Chemistry of Platinum

Following colonisation of South America by the Spanish, many new naturally occurring substances were sent to Europe. One of these was the silvery, unreactive metal, platinum, discovered in New Grenada in the mid-eighteenth century. It was often found in granular form, associated with gold, and the challenge to chemists was to refine it, produce it as wire or sheet, and determine its chemical properties. This interested the professor of chemistry at the University of Edinburgh, Joseph Black, who was able to obtain samples from London-based Spanish contacts, particularly Ignacio Luzuriaga. This paper examines how Black transmitted his knowledge of the metal to large numbers of students attending his annual course.     

Selective Catalytic Isomerization of β-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate

A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO₃]₄ under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.     

Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations

The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.