Detection of Low-Concentration Contaminants in Solution by Exploiting Chemical Derivatization in Surface-Enhanced Raman Spectroscopy

Polymorphism in Sulfadimidine/4-Aminosalicylic Acid Cocrystals: Solid-State Characterization and Physicochemical Properties

Polymorphism of crystalline drugs is a common phenomenon. However, the number of reported polymorphic cocrystals is very limited. In this work, the synthesis and solid-state characterization of a polymorphic cocrystal composed of sulfadimidine (SD) and 4-aminosalicylic acid (4-ASA) is reported for the first time. By liquid-assisted milling, the SD:4-ASA 1:1 form I cocrystal, the structure of which has been previously reported, was formed. By spray drying, a new polymorphic form (form II) of the SD:4-ASA 1:1 cocrystal was discovered which could also be obtained by solvent evaporation from ethanol and acetone. Structure determination of the form II cocrystal was calculated using high-resolution X-ray powder diffraction. The solubility of the SD:4-ASA 1:1 cocrystal was dependent on the pH and predicted by a model established for a two amphoteric component cocrystal. The form I cocrystal was found to be thermodynamically more stable in aqueous solution than form II, which showed transformation to form I. Dissolution studies revealed that the dissolution rate of SD from both cocrystals was enhanced when compared with a physical equimolar mixture and pure SD.

Viscosity and Carbon Dioxide Solubility for LiPF6, LiTFSI, and LiFAP in Alkyl Carbonates: Lithium Salt Nature and Concentration Effect

Water structure and chaotropicity: their uses, abuses and biological implications

The concept of "water structure" has been invoked to explain all manner of aqueous phenomena. Here we look at the origins of this tendency to understand solute hydration in terms of structural changes in bulk water, and consider the validity of one particular example: the classification of small solutes as chaotropic or kosmotropic, and the putative relation of this terminology to notions of structure-making and structure-breaking in the solvent. We doubt whether complex phenomena such as Hofmeister and osmolyte effects on macromolecules can be understood simply on the basis of a change in solvent structure. Rather, we argue that chaotropicity, if understood in the original sense, arises from the activities that solutes exert on macromolecular systems, as well as from deviations of solvation water from bulk-like behaviour. If applied judiciously, chaotropicity remains a potent, biologically pertinent parameter useful for classifying and understanding solution phenomena in all types of living system.

Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)(2)(PPh3)(2) as well as the commercially important metal organic frameworks (MOFs) Cu-3(BTC)(2) (HKUST-1), Zn(2-methylimidazolate)(2) (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h(-1) rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3-4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h(-1). The space time yields (STYs) for these methods of up to 144 x 10(3) kg per m(3) per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.

A study of the kinetic solvent isotope effect on the destruction of microcystin-LR and geosmin using TiO2 photocatalysis

We have previously reported the effectiveness of TiO₂ photocatalysis in the destruction of species generated by cyanobacteria, specifically geosmin and microcystin-LR. In this paper we report an investigation of factors which influence the rate of the toxin destruction at the catalyst surface. A primary kinetic solvent isotope effect of approximately 1.5 was observed when the destruction was performed in a heavy water solvent. This is in contrast to previous reports of a solvent isotope effect of approximately 3, however, these studies were undertaken with a different photocatalyst material. The solvent isotope effect therefore appears to be dependent on the photocatalyst material used. The results of the study support the theory that the photocatalytic decomposition occurs on the catalyst surface rather than in the bulk of the solution. Furthermore it appears that the rate determining step is not oxygen reduction as previously reported. 

Photoelectrochemistry using quinone radical anions

The photoelectrochemistry of quinone radical anions has been demonstrated qualitatively by the photoassisted reduction of methyl viologen with benzoquinone and of neutral red with chloranil. Data were then collected for the estimation of quenching rate constants using Marcus-Weller theory. Reduction potentials of seven quinones were obtained in four solvents (and two aqueous mixtures) by cyclic voltammetry. The solvent effects on these potentials were studied by fitting them to the Taft relationship. The effects of proton donors were also noted. Absorption spectra of the radical anions were measured and the solvent effects noted and commented upon. From the molar absorption coefficients of the radical anions, the mean lifetimes of the excited states were estimated. Fluorescence spectra were obtained for anthraquinone and naphthaquinone radical anions and excitation energies were calculated. These values were estimated for the other quinones. Values of redox potentials for the excited radical anions were thence obtained. The Gibbs energies of the electron transfers between the excited quinone radical anions and the various substrates were obtained and hence the Gibbs energies of activation were calculated using the Marcus equation. The quenching rate constants were calculated using the Rehm-Weller equation and plotted vs. ΔG giving a characteristic Marcus plot including some data in the inverted region. The significance of the inverted region is discussed.

Mathematical modelling of quantum yield enhancements of methyl orange photooxidation in aqueous TiO2 suspensions under controlled periodic UV LED illumination

Quantum yields of the photocatalytic degradation of methyl orange under controlled periodic illumination (CPI) have been modelled using existing models. A modified Langmuir-Hinshelwood (L-H) rate equation was used to predict the degradation reaction rates of methyl orange at various duty cycles and a simple photocatalytic model was applied in modelling quantum yield enhancement of the photocatalytic process due to the CPI effect. A good agreement between the modelled and experimental data was observed for quantum yield modelling. The modified L-H model, however, did not accurately predict the photocatalytic decomposition of the dye under periodic illumination.

Cationic palladium(II) complexes as catalysts for the oxidation of terminal olefins to methyl ketones using hydrogen peroxide.

Ligated Pd(II) complexes have been studied for the catalytic oxidation of terminal olefins to their corresponding methyl ketones. The method uses aqueous hydrogen peroxide as the terminal oxidant; a sustainable and readily accessible oxidant. The choice of ligand, counterion and solvent all have a significant effect on catalytic performance and we were able to develop systems which perform well for these challenging oxidations.

Powder semiconductor photocatalysis in aqueous solution: An overview of kinetics-based reaction mechanisms

A brief, historical overview of 10 apparently different, although in some cases, upon inspection, closely related, popular proposed reaction mechanisms and their associated rate equations, is given and in which the rate expression for each mechanism is derived from basic principles, Appendix A. In Appendix B, each of the 5 main mechanisms are tested using datasets, comprising initial reaction rate vs. organic pollutant concentration, [P] and incident irradiance, ρ, data, reported previously for TiO2, where P is phenol, 4-chlorophenol and formic acid. The best of those tested, in terms of overall fit, simplicity, usefulness and versatility is the disrupted adsorption kinetic model proposed by Ollis. The usual basic assumptions made in constructing these mechanisms are reported and the main underlying concerns explored.

Understanding the Interaction between Low-Energy Electrons and DNA Nucleotides in Aqueous Solution

Reactions that can damage DNA have been simulated using a combination of molecular dynamics and density functional theory. In particular, the damage caused by the attachment of a low energy electron to the nucleobase. Simulations of anionic single nucleotides of DNA in an aqueous environment that was modeled explicitly have been performed. This has allowed us to examine the role played by the water molecules that surround the DNA in radiation damage mechanisms. Our simulations show that hydrogen bonding and protonation of the nucleotide by the water can have a significant effect on the barriers to strand breaking reactions. Furthermore, these effects are not the same for all four of the bases.

Effect of solvent on the hydrogenation of 4-phenyl-2-butanone over Pt based catalysts

The hydrogenation of 4-phenyl-2-butanone over Pt/TiO2 and Pt/SiO2 catalysts has been performed in a range of solvents and it has been observed that the solvent impacted on the selectivity of ketone and aromatic ring hydrogenation as well as the overall TOF of the titania catalyst with no solvent effect on selectivity observed using the silica supported catalyst where ring hydrogenation was favored. For the titania catalyst, alkanes were found to favor ring hydrogenation whereas aromatics and alcohols led to carbonyl hydrogenation. A two-site catalyst model is proposed whereby the aromatic ring hydrogenation occurs over the metal sites while carbonyl hydrogenation is thought to occur predominantly at interfacial sites, with oxygen vacancies in the titania support activating the carbonyl. The effect of the solvent on the hydrogenation reaction over the titania catalyst was related to competition for the active sites between solvent and 4-phenyl-2-butanone.

A kinetic analysis methodology to elucidate the roles of metal, support and solvent for the hydrogenation of 4-phenyl-2-butanone over Pt/TiO2

The rate and, more importantly, selectivity (ketone vs aromatic ring) of the hydrogenation of 4-phenyl-2-butanone over a Pt/TiO2 catalyst have been shown to vary with solvent. In this study, a fundamental kinetic model for this multi-phase reaction has been developed incorporating statistical analysis methods to strengthen the foundations of mechanistically sound kinetic models. A 2-site model was determined to be most appropriate, describing aromatic hydrogenation (postulated to be over a platinum site) and ketone hydrogenation (postulated to be at the platinum–titania interface). Solvent choice has little impact on the ketone hydrogenation rate constant but strongly impacts aromatic hydrogenation due to solvent-catalyst interaction. Reaction selectivity is also correlated to a fitted product adsorption constant parameter. The kinetic analysis method shown has demonstrated the role of solvents in influencing reactant adsorption and reaction selectivity.