Mixed-Metal Hybrid Polyoxometalates with Amino Acid Ligands: Electronic Versatility and Solution Properties.

Eight new members of a family of mixed-metal (Mo,W) polyoxometalates (POMs) with amino acid ligands have been synthesized and investigated in the solid state and solution using multiple physical techniques. While the peripheral POM structural framework is conserved, the different analogues vary in nuclearity of the central metal-oxo core, overall redox state, metal composition, and identity of the zwitterionic α-amino acid ligands. Structural investigations reveal site-selective substitution of Mo for W, with a strong preference for Mo to occupy the central metal-oxo core. This core structural unit is a closed tetrametallic loop in the blue reduced species and an open trimetallic loop in the colorless oxidized analogues. Density functional theory calculations suggest the core as the favored site of reduction and reveal that the corresponding molecular orbital is much lower in energy for a tetra- versus trimetallic core. The reduced species are diamagnetic, each with a pair of strongly antiferromagnetically coupled MoV centers in the tetrametallic core, while in the oxidized complexes all Mo is hexavalent. Solution small-angle X-ray scattering and circular dichroism (CD) studies indicate that the hybrid POM is stable in aqueous solution on a time scale of days within defined concentration and pH ranges, with the stability enhanced by the presence of excess amino acid. The CD experiments also reveal that the amino acid ligands readily exchange with other α-amino acids, and it is possible to isolate the products of amino acid exchange, confirming retention of the POM framework. Cyclic voltammograms of the reduced species exhibit an irreversible oxidation process at relatively low potential, but an equivalent reductive process is not evident for the oxidized analogues. Despite their overall structural similarity, the oxidized and 2e-reduced hybrid POMs are not interconvertible because of the respective open- versus closed-loop arrangement in the central metal-oxo cores.

The nature of the salt error in the Sn(II)-reduced molybdenum blue reaction for determination of dissolved reactive phosphorus in saline waters.

Sn(II) is a well-known reductant used in the formation of phosphomolybdenum blue for the determination of dissolved reactive phosphorus (DRP) in waters because it provides rapid and quantitative reduction. However, in saline waters, this method suffers from a salt error which causes a significant decrease in sensitivity. This phenomenon has never been adequately explained in the literature. The Murphy and Riley method, which uses Sb(III) and ascorbic acid for the reduction step, is preferred for DRP determination in saline waters because it is unaffected by salinity, but it exhibits a sensitivity approximately 30% lower than that when Sn(II) is used as the reductant without Cl(-) interference. This study investigates the processes causing the salt error and possible ways of minimizing it, so that the benefits of Sn(II) reduction on the molybdenum blue reaction rate and sensitivity may be exploited in the determination of low levels of DRP in marine and estuarine waters. It has been established that the salt error is caused by the formation of Sn(IV) chloro-complexes which compete with the formation of Sn(IV)-substituted phosphomolybdenum blue, forcing the reaction to proceed via the much slower, less favourable process of direct reduction that occurs in methods using organic reductants such as ascorbic acid.

The molybdenum blue reaction for the determination of orthophosphate revisited: Opening the black box.

The molybdenum blue reaction, used predominantly for the determination of orthophosphate in environmental waters, has been perpetually modified and re-optimised over the years, but this important reaction in analytical chemistry is usually treated as something of a 'black box' in the analytical literature. A large number of papers describe a wide variety of reaction conditions and apparently different products (as determined by UV-visible spectroscopy) but a discussion of the chemistry underlying this behaviour is often addressed superficially or not at all. This review aims to rationalise the findings of the many 'optimised' molybdenum blue methods in the literature, mainly for environmental waters, in terms of the underlying polyoxometallate chemistry and offers suggestions for the further enhancement of this time-honoured analytical reaction.

The use of on-line UV photoreduction in the flow analysis determination of dissolved reactive phosphate in natural waters.

A highly sensitive flow analysis manifold for rapid determination of dissolved reactive phosphate was developed which uses ethanol and UV light to reduce phosphomolybdic acid, instead of the reactive and short-lived chemical reductants typically employed in molybdenum blue chemistry. This reaction is impractical to perform reproducibly in batch mode, yet is very simple to handle in a flow analysis system and uses a single, very long-lived reagent solution. Interference from common inorganic anions and organic phosphorus species was minimal, and good spike recoveries for a range of sample matrices were obtained. The proposed flow analysis system is characterised by a limit of detection of 1.3 µg L(-1) P, linear range of 5-1000 µg L(-1) P, dynamic range of 5-5000 µg L(-1) P, repeatability of 0.8% (1000 µg L(-1) P, n=10) and 5.6% (10 µg L(-1) P, n=10), and sample throughput of 57 h(-1). It is expected that this method will improve the feasibility of autonomous long-term environmental monitoring of dissolved reactive phosphate using inexpensive apparatus.

Imaging chemical extraction by polymer inclusion membranes using fluorescence microscopy.

Polymer inclusion membranes (PIMs) transport chemicals between bodies of liquid by simultaneously performing chemical extraction and back-extraction. The internal chemical and physical mechanisms by which this transport occurs are, however, poorly understood. Also, some PIMs, which are otherwise optimal for their task, age and lose function after only days, limiting their feasibility for industrial upscaling. Through the application of fluorescence imaging methods we are able for the first time to see where chemical extraction occurs in the membrane. Extraction of fluorescein from solution by PIMs demonstrates inhomogeneities that do not correlate to surface morphology. Fluorescence lifetime imaging demonstrates that regions of increased extraction have distinctly different fluorescence lifetimes to that of the surrounding PIM indicating localized chemical environments, and this is observed to change with membrane age. Fluorescence imaging is shown to allow probing and novel understanding of PIM internal chemical morphology.

The use of a polymer inclusion membrane for separation and preconcentration of orthophosphate in flow analysis.

A highly sensitive flow analysis system has been developed for the trace determination of reactive phosphate in natural waters, which uses a polymer inclusion membrane (PIM) with Aliquat 336 as the carrier for on-line analyte separation and preconcentration. The system operates under flow injection (FI) and continuous flow (CF) conditions. Under optimal FI conditions the system is characterised by a linear concentration range between 0.5 and 1000 µg L(-1)P, a sampling rate of 10h(-1), a limit of detection of 0.5 µgL(-1)P and RSDs of 3.2% (n = 10, 100 µg L(-1)) and 7.7% (n = 10, 10 µg L(-1)). Under CF conditions with 10 min stop-flow time and sample solution flow rate of 1.32 mL min(-1) the flow system offers a limit of detection of 0.04 µg L(-1)P, a sampling rate of 5h(-1) and an RSD of 3.4% (n=5, 2.0 µg L(-1)). Interference studies revealed that anions commonly found in natural waters did not interfere when in excess of at least one order of magnitude. The flow system, operating under CF conditions, was successfully applied to the analysis of natural water samples containing concentrations of phosphate in the low µg L(-1)P range, using the multipoint standard addition method.