Characterization of Silanol Groups in Protonated Magadiite by 1H and 2H Solid-State Nuclear Magnetic Resonance
Silanol groups in protonated magadiite (H-magadiite) were characterized by 1H and 2H solid-state nuclear magnetic resonance (NMR). H-magadiite and deuterated (D) magadiite were synthesized by the treatment of Na-rich magadiite with 0.2 N HC1 and 0.2 N DC1, respectively. In the ’H NMR spectrum measured at room temperature, silanol groups of H-magadiite showed two signals at 3.75 and 5.70 ppm, indicating that two types of silanol groups were present. The ratio of silanol groups associated with strong hydrogen bonding (5.70 ppm) to those with weaker hydrogen bonding (3.75 ppm) was 2 to 1. The 2H NMR spectra of deuterated magadiite were measured in the temperature range from 150 to 440 K. In the spectra measured at temperatures below 294 K, silanol groups showed Pake doublet patterns. These patterns were composed of two components corresponding to the two types of silanol groups shown in the ‘H NMR analysis. Both silanol groups produced wobbling motions with increasing temperature. Above 294 K, the profile of the Pake doublet pattern was transformed gradually to a near triangular pattern, indicating that the silanol groups underwent other motions also, such as a two-site jump.
Synthesis of a liquid zirconium hybrid resin and the ability of the resin to accelerate the curing of a transparent silicone‐modified cycloaliphatic epoxy nanocomposite
A liquid zirconium hybrid resin (Zr–QR) was synthesized through sol-gel reactions of zirconium butoxide with silanol-terminated polydimethylsiloxane (DMS-S12) and γ-glycidoxypropyltrimethoxysilane (Z-6040). The sol-gel reactions were monitored using Fourier transform infrared (FTIR) spectroscopy and proton nuclear magnetic resonance spectroscopy. The Zr–QR morphology was investigated using field emission transmission electron microscopy. The Zr–QR had a well-ordered morphology and the dimensions were less than 5 nm. These properties were achieved because DMS-S12 was used to separate the zirconium clusters and Z-6040 was used to stabilize the Zr–QR. The acceleration of the curing reaction between silicone-modified cycloaliphatic epoxy (SEP) and methylhexahydrophthalic anhydride (MHHPA) caused by the Zr–QR was investigated. Differential scanning calorimetry and FTIR spectroscopy investigations showed that the Zr–QR first reacted with MHHPA, producing chelating ligands and carboxylic acid. Unlike in the conventional method (adding acetic acid to cause non-reactive chelating ligands to form), the carboxylic acid produced effectively accelerated the curing reaction between the SEP and MHHPA. The chelating ligand produced from the Zr–QR and MHHPA suppressed the gelation of the Zr–QR itself during the nanocomposite (SEP–Zr–QR) curing process. The cured SEP–Zr–QR nanocomposite exhibited excellent optical transmittance at visible wavelengths.© 2015 Society of Chemical Industry
The Human Rights Act and Parliamentary Democracy
The Human Rights Act 1998 is the culmination of an aggressive campaign for the incorporation into domestic law of the European Convention on Human Rights, a campaign in which the judges joined forces with other political activists. Variously described as 'brilliant';' 'a masterly exposition of the parliamentary draftsman's art';2 and even 'a thing of intellectual beauty',3 the Act has also been greeted as an 'ingenious compromise' between the 'maximalists' and 'minimalists', the former supporting a judicial power to invalidate legislation, as is the case in Canada.4 But although it is purported to reconcile in 'subtle' form the protection of human rights with the sovereignty of Parliament (a claim even more credible after an important but unsung Commons amendment), the Act also represents an unprecedented transfer of political power from the executive and legislature to the judiciary, and a fundamental re-structuring of our 'political constitution'.s As such it is unquestionably the most significant formal redistribution of political power in this country since 1911,6 and perhaps since 1688 when the Bill of Rights proclaimed loudly that proceedings in Parliament ought not to be questioned or impeached in any court or any other place. In the words of Baroness Williams of Crosby, we have crossed our 'constitutional Rubicon',7 at least to the extent that the courts may now declare a statute incompatible with Convention rights. The enactment of the Human Rights Act 1998 was marked by an unusually high quality of debate, particularly in the House of Lords, with powerful performances by the Lord Chancellor and Lord Lester of Herne Hill. The performance of the latter on one occasion was too much for Lord Campbell of Alloway, unaccustomed it seems to cerebral rather than ceremonial contributions in their Lordships' House. Lord Campbell was heard to protest (in a manner dubbed 'offensive' by Lord Ackner)8 about 'these escoteric lectures on law at this time of night', having 'never heard anything like this after dinner' in the 18 years he had been in the Lords.9 He had better get used to it: the law and the lawyers are about to dominate all the debates, at all times of the day and night, before and after every meal time. Indeed in the Second Reading Debate on this Bill in the House of Lords 'full of