Atomic layer deposition for tuning the surface chemical composition of nickel iron phosphates for oxygen evolution reaction in alkaline electrolyzers.

Transition metal phosphates are promising catalysts for the oxygen evolution reaction (OER) in alkaline medium. Herein, Fe-doped Ni phosphates are deposited using plasma-enhanced atomic layer deposition (PE-ALD) at 300 °C. A sequence offFe phosphate PE-ALD cycles andnNi phosphate PE-ALD cycles is repeatedxtimes. The Fe to Ni ratio can be controlled by the cycle ratio (f/n), while the film thickness can be controlled by the number of cycles (xtimes (n+f)). 30 nm films with an Fe/Ni ratio of ∼10% and ∼37%, respectively, are evaluated in 1.0 M KOH solution. Remarkably, a significant difference in OER activity is found when the order of the Ni and Fe phosphate PE-ALD cycles in the deposition sequence is reversed. A 20%-45% larger current density is obtained for catalysts grown with an Fe phosphate PE-ALD cycle at the end compared to the Ni phosphate-terminated flavour. We attribute this to a higher concentration of Fe centers on the surface, as a consequence of the specific PE-ALD approach. Secondly, increasing the thickness of the catalyst films up to 160 nm results in an increase of the OER current density and active surface area, suggesting that the as-deposited smooth and continuous films are converted into electrolyte-permeable structures during catalyst activation and operation. This work demonstrates the ability of PE-ALD to control both the surface and bulk composition of thin film electrocatalysts, offering valuable opportunities to understand their impact on performance.

Electromotive Enhanced Drug Administration in Oncology: Principles, Evidence, Current and Emerging Applications.

Local-regional administration of cytotoxic drugs is an important adjunct to systemic chemotherapy amongst cancer patients. It allows for targeted delivery of agents at high concentration to target sites while minimizing systemic side effects. Despite the pharmacokinetic advantages of the local-regional approach, drug transport into tumor nodules remains limited due to the biophysical properties of these tissues. Electromotive enhanced drug administration (EMDA) represents a potential solution to overcome challenges in local drug transport by applying electric currents. Through electrokinetic phenomena of electromigration, electroosmosis and electroporation, electric currents have been shown to improve drug penetration and distribution in a wide variety of clinical applications. Amongst patients with non-muscular invasive bladder cancer (NMIBC) and basal and squamous cell skin cancers, EMDA has been successfully adopted and proven efficacious in several pre-clinical and clinical studies. Its application in ophthalmological and other conditions has also been explored. This review provides an overview of the underlying principles and factors that govern EMDA and discusses its application in cancer patients. We also discuss novel EMDA approaches in pre-clinical studies and explore future opportunities of developments in this field.

Synchrotron X-ray diffraction investigation of the surface condition of artefacts from King Henry VIII's warship the Mary Rose.

Synchrotron X-ray diffraction (XRD) measured on the XMaS beamline at the ESRF was used to characterize the alloy composition and crystalline surface corrosion of three copper alloy Tudor artefacts recovered from the undersea wreck of King Henry VIII's warship the Mary Rose. The XRD method adopted has a dynamic range ∼1:105 and allows reflections <0.002% of the height of major reflections in the pattern to be discerned above the background without smoothing. Laboratory XRD, scanning electron microscopy-energy dispersive spectroscopy, synchrotron X-ray fluorescence and X-ray excited optical luminescence-X-ray near-edge absorption structure were used as supporting techniques, and the combination revealed structural and compositional features of importance to both archaeology and conservation. The artefacts were brass links believed to be fragments of chainmail and were excavated from the seabed during 1981 and 1982. Their condition reflects very different treatment just after recovery, viz. complete cleaning and conservation, chemical corrosion inhibition and chloride removal only, and distilled water soaking only (to remove the chlorides). The brass composition has been determined for all three at least in the top 7 µm or so as Cu(73%)Zn(27%) from the lattice constant. Measurement of the peak widths showed significant differences in the crystallite size and microstrain between the three samples. All of the links are found to be almost chloride-free with the main corrosion products being spertiniite, sphalerite, zincite, covellite and chalcocite. The balance of corrosion products between the links reflects the conservation treatment applied to one and points to different corrosion environments for the other two.

The metamorphosis of analytical chemistry.

Defining analytical chemistry as the measurement of isolated compositional features in a selected study object ignores the unique perspective that analytical chemists bring to twenty-first century science and society. In this feature article, we will discuss some of the existing preconceptions and misinterpretations of analytical chemistry that occur at present and will tackle them from the more up-to-date perspective of science in the Big Data Era. This will place their influence in context while simultaneously enlarging the scope of the discipline analytical chemistry to its well-deserved prevalent position in present-day science and technology. Graphical abstract.