The Scottish Parliament in the 15th and 16th centuries

Earlier histories of the Scottish parliament have been somewhat constitutional in emphasis and have been exceedingly critical of what was understood to be parliament's subservience to the crown. Estimates by constitutional historians of the extreme weakness of parliament rested on an assessment of the constitutional system. The argument was that many of its features were not consistent with a reasonably strong parliament. Because the 'constitution' is apparently fragmented, with active roles played by bodies such as the lords of articles, the general council and the convention of estates, each apparently suggesting that parliament was inadequate, historians have sometimes failed to appreciate the positive role played by the estates in the conduct of national affairs. The thesis begins with a discussion of the reliability of the printed text of APS and proceeds to an examination of selected aspects of the work of parliament in a period from c 1424-c 1625. The belief of constitutional historians such as Rait that conditions In Scotland proved unfavourable to the interests and. effectiveness of parliament in the fifteenth and sixteenth centuries, is also examined. Chapter 1 concludes that APS is a less than reliable text, particularly for the reign of James I. Numerous statutes were excluded from the printed text and they are offered below for the first time. These statutes have been a useful addition to our understanding of the reign of James I. Chapter 2 analyses the motives behind the schemes for shire representation and concludes that neither constitutional theory nor political opportunism explains the support which James I and James VI gave to these measures. Both these monarchs were motivated by the realisation that their particular ambitions were dependent on winning the support of the estates whose ranks should include representatives from the shires. Chapter 3 examines the method of electing the lords of articles, the composition of this committee, and some aspects of its operation. The conclusion is that in the main the estates were the deciding force in the choice of the lords of articles. The committee's composition was more a reflection of a desire for a balance between representatives from north and south of the Forth and for the most important burghs and clergy to be selected than an attempt at electing government favourites. The articles did exercise a significant control over the items which came before parliament but this control was not absolute and applied to government as well as private legislation. Chapter 4 questions the traditional view that the general council and convention of estates were the same body. It is argued that they were two different institutions with different powers, but that they nevertheless worked within certain limits and were careful not to usurp the authority of parliament. Chapter 5 concedes that taxation was sometimes decided outside parliament; that the irregularity of taxation certainly weakened the bargaining power of the estates and that the latter did not appear to capitalise on these occasions when taxation was an issue. But the tendency was to ensure that, whether in or out of parliament, the decision to impose taxation was taken by a large number of each estate. The infrequency of taxation was a direct consequence of an unwillingness among the estates to agree to a regular taxation and their preference to ensure for the crown an alternative source of income. Moreover taxation was one issue, which more than any other, would be subject to contentious opposition by the estates, and could lead to the crown's defeat. Chapter 6 is concerned with ecclesiastical representation after the Reformation and the church's attitudes to the possibility of ministerial representation. Some ministers had doctrinal misgivings but the majority came to believe that the church's absence from parliament bad severely reduced. the influence of the church. That no agreement was forthcoming on a system of ministerial representation, particularly after 1597, is attributable to the estates' unwillingness to compromise and, not to the strength of opposition in the church. Chapter 7 examines the institutions which are sometime seen as 'rivals' of parliament and concludes that institutions such as the privy council were generally very careful in matters which needed the approval of parliament, and seemed aware of the greater authority of parliament. Chapter 8 which illustrates how parliament had the right to be consulted in all important matters of state, brings together the main points of the earlier chapters and offers further illustrations of the essential role which parliament played in the conduct of national affairs. Whether or not the system can be regarded as constitutionally sound, the estates in Scotland could observe parliament's day-to-day operation with some satisfaction. All in all, there is little convincing evidence that parliament was as weak as some historians would have us believe.

Exploring coordination-driven self-assembly with autonomous chemical robots

The work presented herein focused on the automation of coordination-driven self assembly, exploring methods that allow syntheses to be followed more closely while forming new ligands, as part of the fundamental study of the digitization of chemical synthesis and discovery. Whilst the control and understanding of the principle of pre-organization and self-sorting under non-equilibrium conditions remains a key goal, a clear gap has been identified in the absence of approaches that can permit fast screening and real-time observation of the reaction process under different conditions. A firm emphasis was thus placed on the realization of an autonomous chemical robot, which can not only monitor and manipulate coordination chemistry in real-time, but can also allow the exploration of a large chemical parameter space defined by the ligand building blocks and the metal to coordinate. The self-assembly of imine ligands with copper and nickel cations has been studied in a multi-step approach using a self-built flow system capable of automatically controlling the liquid-handling and collecting data in real-time using a benchtop MS and NMR spectrometer. This study led to the identification of a transient Cu(I) species in situ which allows for the formation of dimeric and trimeric carbonato bridged Cu(II) assemblies. Furthermore, new Ni(II) complexes and more remarkably also a new binuclear Cu(I) complex, which usually requires long and laborious inert conditions, could be isolated. The study was then expanded to the autonomous optimization of the ligand synthesis by enabling feedback control on the chemical system via benchtop NMR. The synthesis of new polydentate ligands has emerged as a result of the study aiming to enhance the complexity of the chemical system to accelerate the discovery of new complexes. This type of ligand consists of 1-pyridinyl-4-imino-1,2,3-triazole units, which can coordinate with different metal salts. The studies to test for the CuAAC synthesis via microwave lead to the discovery of four new Cu complexes, one of them being a coordination polymer obtained from a solvent dependent crystallization technique. With the goal of easier integration into an automated system, copper tubing has been exploited as the chemical reactor for the synthesis of this ligand, as it efficiently enhances the rate of the triazole formation and consequently promotes the formation of the full ligand in high yields within two hours. Lastly, the digitization of coordination-driven self-assembly has been realized for the first time using an in-house autonomous chemical robot, herein named the ‘Finder’. The chemical parameter space to explore was defined by the selection of six variables, which consist of the ligand precursors necessary to form complex ligands (aldehydes, alkineamines and azides), of the metal salt solutions and of other reaction parameters – duration, temperature and reagent volumes. The platform was assembled using rounded bottom flasks, flow syringe pumps, copper tubing, as an active reactor, and in-line analytics – a pH meter probe, a UV-vis flow cell and a benchtop MS. The control over the system was then obtained with an algorithm capable of autonomously focusing the experiments on the most reactive region (by avoiding areas of low interest) of the chemical parameter space to explore. This study led to interesting observations, such as metal exchange phenomena, and also to the autonomous discovery of self assembled structures in solution and solid state – such as 1-pyridinyl-4-imino-1,2,3-triazole based Fe complexes and two helicates based on the same ligand coordination motif.