Enhanced Photoacoustic Visualisation of Clinical Needles by Combining Interstitial and Extracorporeal Illumination of Elastomeric Nanocomposite Coatings.

Ultrasound (US) image guidance is widely used for minimally invasive procedures, but the invasive medical devices (such as metallic needles), especially their tips, can be poorly visualised in US images, leading to significant complications. Photoacoustic (PA) imaging is promising for visualising invasive devices and peripheral tissue targets. Light-emitting diodes (LEDs) acting as PA excitation sources facilitate the clinical translation of PA imaging, but the image quality is degraded due to the low pulse energy leading to insufficient contrast with needles at deep locations. In this paper, photoacoustic visualisation of clinical needles was enhanced by elastomeric nanocomposite coatings with superficial and interstitial illumination. Candle soot nanoparticle-polydimethylsiloxane (CSNP-PDMS) composites with high optical absorption and large thermal expansion coefficients were applied onto the needle exterior and the end-face of an optical fibre placed in the needle lumen. The excitation light was delivered at the surface by LED arrays and through the embedded optical fibre by a pulsed diode laser to improve the visibility of the needle tip. The performance was validated using an ex-vivo tissue model. An LED-based PA/US imaging system was used for imaging the needle out-of-plane and in-plane insertions over approach angles of 20 deg to 55 deg. The CSNP-PDMS composite conferred substantial visual enhancements on both the needle shaft and the tip, with an average of 1.7- and 1.6-fold improvements in signal-to-noise ratios (SNRs), respectively. With the extended light field involving extracorporeal and interstitial illumination and the highly absorbing coatings, enhanced visualisation of the needle shaft and needle tip was achieved with PA imaging, which could be helpful in current US-guided minimally invasive surgeries.

CuInS2 Quantum Dot and Polydimethylsiloxane Nanocomposites for All-Optical Ultrasound and Photoacoustic Imaging.

Dual-modality imaging employing complementary modalities, such as all-optical ultrasound and photoacoustic imaging, is emerging as a well-suited technique for guiding minimally invasive surgical procedures. Quantum dots are a promising material for use in these dual-modality imaging devices as they can provide wavelength-selective optical absorption. The first quantum dot nanocomposite engineered for co-registered laser-generated ultrasound and photoacoustic imaging is presented. The nanocomposites developed, comprising CuInS2 quantum dots and medical-grade polydimethylsiloxane (CIS-PDMS), are applied onto the distal ends of miniature optical fibers. The films exhibit wavelength-selective optical properties, with high optical absorption (> 90%) at 532 nm for ultrasound generation, and low optical absorption (< 5%) at near-infrared wavelengths greater than 700 nm. Under pulsed laser irradiation, the CIS-PDMS films generate ultrasound with pressures exceeding 3.5 MPa, with a corresponding bandwidth of 18 MHz. An ultrasound transducer is fabricated by pairing the coated optical fiber with a Fabry-Pérot (FP) fiber optic sensor. The wavelength-selective nature of the film is exploited to enable co-registered all-optical ultrasound and photoacoustic imaging of an ink-filled tube phantom. This work demonstrates the potential for quantum dots as wavelength-selective absorbers for all-optical ultrasound generation.

Proton Chelating Ligands Drive Improved Chemical Separations for Rhodium.

Current methods for the extraction of rhodium carry the highest carbon footprint and worst pollution metrics of all of the elements used in modern technological applications. Improving upon existing methods is made difficult by the limited understanding of the molecular-level chemistry occurring in extraction processes, particularly in the hydrometallurgical separation step. While many of the precious metals can be separated by solvent extraction, there currently exist no commercial extractants for Rh. This is due to its complicated mixed speciation upon leaching into hydrochloric acid, which gives rise to difficulties in designing effective reagents for solvent extraction. Herein we show that the diamidoamine reagent N- n-hexylbis( N-methyl- N- n-octylethylamide)amine transports Rh(III) from aqueous HCl into an organic phase as the monoaquated dianion [RhCl5(H2O)]2- through the formation of an outer-sphere assembly; this assembly has been characterized by experimentation (slope analysis, FT-IR and NMR spectroscopy, EXAFS, SANS, and ESI-MS) and computational modeling. The paper demonstrates the importance of applying a broad range of techniques to obtain a convincing mode of action for the complex processes involved in anion recognition in the solution phase. A consistent and comprehensive understanding of how the ligand operates to achieve Rh(III) selectivity over the competitor anion Cl- has emerged. This knowledge will guide the design of extractants and thus offers promise for improving the sustainability of metal extraction from both traditional mining sources and the recycling of secondary source materials.

EPR/ENDOR and Computational Study of Outer Sphere Interactions in Copper Complexes of Phenolic Oximes.

Copper complexes of the phenolic oxime family of ligands (3-X-salicylaldoximes) are used extensively as metal solvent extractants. Incorporation of electronegative substituents in the 3-position, ortho to the phenol group, can be used to buttress the interligand H-bonding, leading to an enhancement in extractant strength. However, investigation of the relevant H-bonding in these complexes can be exceedingly difficult. Here, we have combined EPR, ENDOR, DFT, and X-ray crystallography to study this effect. Analysis of the (1)H ENDOR data revealed a variation in the Cu···H(16) (oxime proton) distance from 2.92 Å for the unsubstituted complex [Cu(L(2))2] to 3.65 Å for the X = CH2N(C6H13)2 substituted complex [Cu(L(3))2]. DFT calculations showed that this variation is caused by changes to the length and strength of the H-bond between the oximic hydrogen and the phenolate oxygen. Noticeable changes to the Cu···H(15) (azomethine proton) distances and the Cu···N bonding parameters were also observed in the two complexes, as revealed through the (N)A and (N)Q ENDOR data. Distortions in the structure of the complex and variations in the oximic proton to phenolate oxygen H-bond strength caused by the substituent (X) were confirmed by DFT and X-ray crystallography. DFT directly evidenced the importance of the interaction between H(16) and the amine nitrogen of CH2N(C6H13)2 in the buttressed complex and indicated that the high strength of this interaction may not necessarily lead to an enhancement of copper extraction, as it can impose an unfavorable geometry in the inner coordination sphere of the complex. Therefore, ENDOR, DFT, and X-ray structural data all indicate that the aminomethyl substituent (X) ortho to the phenolic oxygen atom provides a particularly strong buttressing of interligand H-bonding in these copper complexes and that these outer sphere interactions can significantly influence structure and stability.

Anion Receptor Design: Exploiting Outer-Sphere Coordination Chemistry To Obtain High Selectivity for Chloridometalates over Chloride.

High anion selectivity for PtCl6(2-) over Cl(-) is shown by a series of amidoamines, R(1)R(2)NCOCH2CH2NR(3)R(4) (L1 with R(1) = R(4) = benzyl and R(2) = R(3) = phenyl and L3 with R(1) = H, R(2) = 2-ethylhexyl, R(3) = phenyl and R(4) = methyl), and amidoethers, R(1)R(2)NCOCH2CH2OR(3) (L5 with R(1) = H, R(2) = 2-ethylhexyl and R(3) = phenyl), which provide receptor sites which extract PtCl6(2-) preferentially over Cl(-) in extractions from 6 M HCl solutions. The amidoether receptor L5 was found to be a much weaker extractant for PtCl6(2-) than its amidoamine analogues. Density functional theory calculations indicate that this is due to the difficulty in protonating the amidoether to generate a cationic receptor, LH(+), rather than the latter showing weaker binding to PtCl6(2-). The most stable forms of the receptors, LH(+), contain a tautomer in which the added proton forms an intramolecular hydrogen bond to the amide oxygen atom to give a six-membered proton chelate. Dispersion-corrected DFT calculations appear to suggest a switch in ligand conformation for the amidoamine ligands to an open tautomer state in the complex, such that the cationic N-H or O-H groups are also readily available to form hydrogen bonds to the PtCl6(2-) ion, in addition to the array of polarized C-H bonds. The predicted difference in energies between the proton chelate and nonchelated tautomer states for L1 is small, however, and the former is found in the X-ray crystal structure of the assembly [(L1H)2PtCl6]. The DFT calculations and the X-ray structure indicate that all LH(+) receptors present an array of polarized C-H groups to the large, charge diffuse PtCl6(2-) anion resulting in high selectivity of extraction of PtCl6(2-) over the large excess of chloride.

Polyacidic multiloading metal extractants.

Novel polynucleating, di- and tri-acidic ligands have been designed to increase the molar and mass transport efficiencies for the recovery of base metals by solvent extraction.

The assembly of rotaxane-like dye/cyclodextrin/surface complexes on aluminium trihydroxide or goethite.

Simple azo-dyes carrying phosphonic acid and arsonic acid substituents such as 4-(4-hydroxyphenyl azo)phenylphosphonic acid (5) and 4-(4-hydroxyphenylazo)phenylarsonic acid (6) bind more strongly to high surface area oxides such as aluminium trihydroxide and goethite than their carboxylic and sulfonic acid analogues and the phosphonate-functionalized dyes have been shown to have greater humidity fastness when printed onto commercial alumina-coated papers. Adsorption isotherm measurements provide evidence for the formation of ternary dye/cyclodextrin/surface complexes. Dyes which form such ternary complexes show higher light fastness when printed onto alumina coated papers in an ink formulation containing alpha-cyclodextrin.