Preservation of York Minster historic limestone by hydrophobic surface coatings

Magnesian limestone is a key construction component of many historic buildings that is under constant attack from environmental pollutants notably by oxides of sulfur via acid rain, particulate matter sulfate and gaseous SO 2 emissions. Hydrophobic surface coatings offer a potential route to protect existing stonework in cultural heritage sites, however, many available coatings act by blocking the stone microstructure, preventing it from 'breathing' and promoting mould growth and salt efflorescence. Here we report on a conformal surface modification method using self-assembled monolayers of naturally sourced free fatty acids combined with sub-monolayer fluorinated alkyl silanes to generate hydrophobic (HP) and super hydrophobic (SHP) coatings on calcite. We demonstrate the efficacy of these HP and SHP surface coatings for increasing limestone resistance to sulfation, and thus retarding gypsum formation under SO/H O and model acid rain environments. SHP treatment of 19th century stone from York Minster suppresses sulfuric acid permeation.

Identifying the active phase in Cs-promoted MgO nanocatalysts for triglyceride transesterification

Background: Biodiesel is a clean-burning, renewable and biodegradable diesel fuel substitute derived from animal fats and plant oils, which may play an important role in replacing diminishing fossil fuel reserves and combating climate change. Conventional biodiesel production uses soluble base catalysts, such as Na or K alkoxides, to convert oils into fuel, and as a result requires energy intensive aqueous quench cycles to isolate the biodiesel product. Results: Cs-doping nanoparticulate MgO, prepared via a novel, supercritical sol-gel method, yields a solid base catalyst with improved activity for the transesterification of pure triacylglycerides (TAGs) and olive oil. Conclusion: Here, X-ray absorption spectroscopy (XAS) is used to probe the local chemical environment of Cs atoms in order to identify the nature of the catalytically active species as CsMg(CO)(HO). © 2013 Society of Chemical Industry.

Warfarin toxicity: do discharge ICD-10 codes and yellow cards accurately identify serious adverse drug reactions?

Focal points: ICD-10 codings and spontaneous yellow card reports for warfarin toxicity were compared retrospectively over a one-year period Eighteen cases of ICD-10 coded warfarin toxicity were identified from a total of 55,811 coded episodes More than three times as many ADRs to warfarin were found by screening ICD-10 codes as were reported spontaneously using the yellow card scheme Valuable information is being lost to regulatory authorities and as recognised reporters to the yellow card scheme, pharmacists are well placed to report these ADRs, enhancing their role in the safe and appropriate prescribing of warfarin

Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites:fact or fiction?

Nanoparticulate gold has emerged as a promising catalyst for diverse mild and efficient selective aerobic oxidations. However, the mechanism of such atom-economical transformations, and synergy with functional supports, remains poorly understood. Alkali-free Mg-Al hydrotalcites are excellent solid base catalysts for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA), but only in concert with high concentrations of metallic gold nanoparticles. In the absence of soluble base, competitive adsorption between strongly-bound HMF and reactively-formed oxidation intermediates site-blocks gold. Aqueous NaOH dramatically promotes solution phase HMF activation, liberating free gold sites able to activate the alcohol function within the metastable 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) reactive intermediate. Synergistic effects between moderate strength base sites within alkali-free hydrotalcites and high gold surface concentrations can afford highly selective and entirely heterogeneous catalysts for aqueous phase aldehyde and alcohol cascade oxidations pertinent to biomass transformation.

The Romanian Orthodox Church

At first glance, the nationalist ideology of the French Revolution seems to have had little impact on the Orthodox Church in Romanian-speaking territories. Romanians were the predominant inhabitants of the principalities of Wallachia and Moldavia and the neighboring territories of Transylvania (including Crişana, Maramureş and Banat), Bukovina, Bessarabia, and Dobrudja. The majority of ethnic Romanians belonged to the Orthodox faith while their communities were at the intersection of geopo liti cal interests of the Rus sian, Ottoman, and Habsburg empires. In 1859 the Principalities of Wallachia and Moldavia (known as the Old Kingdom between 1866 and 1918) united into a single state under the rule of a local prince. The term "Romania" began to be used by the new state in its of cial documents in 1862. Two years later, the state supported the declaration of a Romanian autocephalous (in de pen dent) church that was recognized by the Ecumenical Patriarchate in 1885. As an integrative part of the Orthodox commonwealth, the church was situated between the competing jurisdictions of the Ecumenical Patriarchate and the Rus sian Orthodox Church, while its declaration of autocephaly followed a pattern in the spread of national churches in Southeastern Europe. From the Treaty of Kuchuk Kainardji of 1774 to the beginning of the Greek War for In de pen dence in 1821, the Romanian principalities were under the suzerainty of the Ottoman Empire, which had full control of their po liti cal and economic affairs. The sultan appointed princes, and the Porte determined their po liti cal and judicial status. The princes were drawn from the "Phanariots," and were directly appointed by the Porte from preponderantly Greek elite rather than the Romanian local elite, the boyars (boieri).1 In each principality, the church was headed by a metropolitan who was under the direct jurisdiction of the Ecumenical Patriarchate. That religion mattered to local population as a means of social cohesion was suggestively depicted by Anatole de Demidoff, an En glish traveler in the region in 1837. Arriving in Bucharest, the capital of Wallachia, he claimed that: I know of no city in Europe in which it is possible to find more agreeable society, or in which there is a better tone, united with the most charming gaiety⋯. Religion, which is here of the schismatic Greek creed, does not, properly speaking, hold any great empire over the minds of the Wallachian people, but they observe its outward forms, and particularly the austerities of fasting, with scrupulous exactitude. The people are seen to attend divine ser vice with every sign of respect, and the great number of churches existing in Wallachia, bear witness to the ardent zeal with which outward worship is honored.2 The Romanian Orthodox Church was a national institution, closely linked to social, economic, and po liti cal structures. In most cases, Orthodox hierarchs were appointed from the families of boyars, thus ensuring a close relationship with the state authorities and its policies. As one of the largest landowners in the principalities, the church had a prime role in administrating healthcare and education. Although the majority of the clergy was uneducated, it dispensed both ecclesiastical and civil justice and in many cases worked closely with boyars in local administration.3 The lower clergy not only contributed directly to the economy but also benefited from tax privileges. Some small villages had an unusually high proportion of clergy in comparison to the overall population. For example, in 1810, Stənisləveşti, a village in the south of Wallachia, was composed of eleven houses and had two priests, five deacons, and three cantors; similarly, the Frəsinet village of nineteen houses had two priests and five deacons.4 Although these cases were exceptional, they indicate both the economic value of being a member of the clergy and the wider canonical dimension of church jurisdiction. The special status of the clergy was reflected not only at lower but also at higher levels. Bishops and metropolitans engaged with state policy and in many cases opposition to the authorities led to the loss of a spiritual seat. The metropolitan of each principality worked with the prince and was president of the divan, the gathering of all boyars. He held the right to be the first person to comment on state policy and to make recommendations when the prince was absent. The metropolitan replaced the prince when the principality had no political ruler, such as in the cases of Metropolitan Veniamin Costachi of Moldavia in 1806 and Metropolitan Dositei Filitti of Wallachia, while the bishops of Buzəu and Argeş were members of the provisional government during the Rus sian occupation of the principalities in 1808. The higher clergy had both religious and political prerogatives in relation to foreign powers as evident in their heading of the boyars' delegation to peace negotiation between the Rus sian and Ottoman empires at Focşani in 1772 and addressing memoranda to the Austrian and Rus sian governments in 1802.5 The primary role of the church in the principalities of Moldavia and Wallachia was paralleled by the national mobilization of Orthodox communities in the neighboring territories that had Romanian inhabitants. Although throughout the region Orthodox communities were incorporated into church structures as part of the Habsburg, Austrian or Rus sian empires, the nineteenth century was characterized by the leadership's search for political autonomy and the building of a Romanian national identity. The Orthodox communities outside the Old Kingdom maintained relations with the faithful in principalities across the Carpathian Mountains and the Dniester River and sought support in their struggle for political and religious rights.