The thermodynamic properties of 154 mineral end-members, 13 silicate liquid end-members and 22 aqueous fluid species are presented in a revised and updated data set. The use of a temperature-dependent thermal expansion and bulk modulus, and the use of high-pressure equations of state for solids and fluids, allows calculation of mineral–fluid equilibria to 100 kbar pressure or higher. A pressure-dependent Landau model for order–disorder permits extension of disordering transitions to high pressures, and, in particular, allows the alpha–beta quartz transition to be handled more satisfactorily. Several melt end-members have been included to enable calculation of simple phase equilibria and as a first stage in developing melt mixing models in NCKFMASH. The simple aqueous species density model has been extended to enable speciation calculations and mineral solubility determination involving minerals and aqueous species at high temperatures and pressures. The data set has also been improved by incorporation of many new phase equilibrium constraints, calorimetric studies and new measurements of molar volume, thermal expansion and compressibility. This has led to a significant improvement in the level of agreement with the available experimental phase equilibria, and to greater flexibility in calculation of complex mineral equilibria. It is also shown that there is very good agreement between the data set and the most recent available calorimetric data.

An internally consistent thermodynamic data set for phases of petrological interest

The thermodynamic properties of 154 mineral end-members, 13 silicate liquid end-members and 22 aqueous fluid species are presented in a revised and updated data set. The use of a temperature-dependent thermal expansion and bulk modulus, and the use of high-pressure equations of state for solids and fluids, allows calculation of mineral-fluid equilibria to 100 kbar pressure or higher. A pressure-dependent Landau model for order-disorder permits extension of disordering transitions to high pressures, and, in particular, allows the alpha-beta quartz transition to be handled more satisfactorily. Several melt end- members have been included to enable calculation of simple phase equilibria and as a first stage in developing melt mixing models in NCKFMASH. The simple aqueous species density model has been extended to enable speciation calculations and mineral solubility determination involving minerals and aqueous species at high temperatures and pressures. The data set has also been improved by incorporation of many new phase equilibrium constraints, calorimetric studies and new measurements of molar volume, thermal expansion and compressibility. This has led to a significant improvement in the level of agreement with the available experimental phase equilibria, and to greater flexibility in calculation of complex mineral equilibria. It is also shown that there is very good agreement between the data set and the most recent available calorimetric data. kinetics which apply to determining directly the greatest majority of such equilibria in the laboratory, for forming solid solutions, and inclusion of aqueous and silicate melt species), and provides uncertainties especially at lower temperatures, as well as the diYculty of establishing reversals of reactions involving solid allowing the likely uncertainties on the results of thermodynamic calculations to be estimated. This is a solutions. The levels of precision and accuracy required of thermodynamic data in order to be able to forward- critical issue in that calculations using data sets should always involve uncertainty propagation to help evalu- model synthetic and natural mineral assemblages mean that the continuing upgrading and expansion of the ate the results. Because the experimental phase equilib- ria involve overlapping subsets of compositional space, data set by incorporation of new phase equilibrium constraints, calorimetry and new measurements of the derived thermodynamic data are highly correlated, and it is only the inclusion of the correlations which molar volume, thermal expansion and compressibility are more than justified. enables the reliable calculation of uncertainties on mineral reactions to be performed. Earlier work on mineral thermodynamic data sets for rock-forming minerals includes compilations of The thermodynamic data extraction involves using weighted least squares on the diVerent types of data

Introduction: The globalization of the pharmaceutical supply chain has introduced new challenges, chief among them, fighting the international criminal trade in fake medicines. As the manufacture, ...

A review of existing and emerging digital technologies to combat the global trade in fake medicines

Characterization of permeability and sorption in Matrimid/C60 mixed matrix membranes

The adulteration and fraudulent manufacture of medicines is an old problem, vastly aggravated by modern manufacturing and trade. In the last decade, impotent antimicrobial drugs have compromised the treatment of many deadly diseases in poor countries. More recently, negligent production at a Massachusetts compounding pharmacy sickened hundreds of Americans. While the national drugs regulatory authority (hereafter, the regulatory authority) is responsible for the safety of a country's drug supply, no single country can entirely guarantee this today.The once common use of the term counterfeit to describe any drug that is not what it claims to be is at the heart of the argument. In a narrow, legal sense a counterfeit drug is one that infringes on a registered trademark. The lay meaning is much broader, including any drug made with intentional deceit. Some generic drug companies and civil society groups object to calling bad medicines counterfeit, seeing it as the deliberate conflation of public health and intellectual property concerns. Countering the Problem of Falsified and Substandard Drugs accepts the narrow meaning of counterfeit, and, because the nuances of trademark infringement must be dealt with by courts, case by case, the report does not discuss the problem of counterfeit medicines.

Countering the Problem of Falsified and Substandard Drugs

Tetrahedral and octahedral ordering in synthetic elinochlore with compositions (MgsAI)[Si3Al]OIO(OH). and (Mg...56AII.44)[Si2s.AI1.42]OIO(OH). have been studied by 29Si, 27 AI, and IH MAS NMR spectroscopy. The 29Sispectra indicate that AI-O-AI avoidance occurs on tetrahedral sites with considerable short-range order in accordance with the Homogeneous Dispersion of Charges (HOC) model of Herrero et ai. (1985a), in which charge imbalance within the tetrahedral sheets is minimized. The

A multinuclear NMR study of clinochlore

We report the progress of a project at King’s College London funded by UK Healthcare Charity, the Wellcome Trust, to develop a prototype, portable medicines authentication device based on nuclear quadrupole resonance spectroscopy (NQR) and employing innovative parametric data processing, for the non-invasive, non-destructive and quantitative inspection of packaged medicines. The first-generation system will target nitrogen- and/or chlorine-containing medicines in blister packs and bottles without the need to remove these items from their packaging. Initial proof of principle will be based around a database consisting of the NQR “fingerprints” of a select list of essential medicines as defined by the World Health Organization that are commonly counterfeited in developing countries. This database will be expanded as the project progresses, and as the device is taken up for commercialization.

The Emerging Field of Medicines Authentication by Nuclear Quadrupole Resonance Spectroscopy

The development of a system for the detection of ammonium nitrate (AN) in vehicles by nuclear quadrupole resonance (NQR) is described. The results from studies of the penetration of radiofrequency (RF) magnetic fields inside certain metal enclosures, including full-scale vehicles, were critical in the design of a novel high-Q resonant probe. The probe was shaped not only for optimal penetration of RF magnetic fields into vehicles, but also for optimal rejection of RF interference and ease of shielding. A full-scale technical demonstrator was designed, built and successfully demonstrated, using novel pulse sequences to generate and detect NQR signals from AN concealed within the boot (trunk) of a car and in the loading bay of a (metal-sided) van. Among the key technical advances that made possible the effective operation of this system was the development of pulse sequences that generate detectable NQR responses for RF magnetic fields that are both very weak and very inhomogeneous.

Detection of ammonium nitrate inside vehicles by nuclear quadrupole resonance

Stable van der Waals-bonded C60/benzene solvates were prepared using a novel crystallization technique. Solid-state NMR measurements on highly crystalline solvate under liquid benzene show that there is very little interaction between benzene and the C60 molecules and that the rotation of C60 at room temperature is not hindered. The magnetization transfer between benzene protons and local C60 molecules is highly inefficient. Three benzene species have been found in the solvate:  two, nearly freely mobile, in wide and narrow porous structures, and the third constrained by C60 molecules in lattice defects. Premelting of deuterated benzene within the C60 solvate has been observed at Tm − 10.5 K.

Solid-State NMR Studies of Fullerene C60/Benzene Solvates

27 Al and 29Si MAS and CP MAS NMR have been used to monitor structural modifications of mordenite subjected to hydrothermal dealumination, acid leaching and calcination. Six, four- and possibly five-coordinate extraframework aluminium species are formed upon expulsion of aluminium from the framework. 1H–29Si CP MAS NMR monitors the creation of Si—OH defect sites. Calcination of dealuminated mordenite greatly reduces the number of such defects, indicating that they are substantially ‘healed’ by silicon atoms from other parts of the crystal, and also via dehydration of hydroxy groups to form bridging oxygen sites. The occupancies of crystallographically inequivalent Si(0AI) sites calculated from 29Si MAS NMR spectra of dealuminated mordenite show that aluminium atoms occupy some of the T2 tetrahedral sites in the parent material.

Jamie Barras

Papers

A multinuclear NMR study of clinochlore

The Emerging Field of Medicines Authentication by Nuclear Quadrupole Resonance Spectroscopy

Detection of ammonium nitrate inside vehicles by nuclear quadrupole resonance

Solid-State NMR Studies of Fullerene C60/Benzene Solvates

27 Al and 29Si solid-state NMR studies of dealuminated mordenite