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A simple approach to the delamination of PVDF bound graphite anode material from electric vehicle batteries is presented. This recovered graphite shows good electrochemical performance after a short low temperature thermal treatment.

Seebeck measurements of n-type amorphous germanium telluride thin films (100 nm) containing oxygen and implanted with Bismuth (Bi) have been studied under dark and monochromatic light conditions from 1800 to 400 nm. The Bi-doped film has a negative Seebeck coefficient indicating its n-type nature that results from the implantation compared to the p-type undoped films. Upon illumination with monochromatic light across the near-infrared and visible region the magnitude of the measured Seebeck voltage increases (becomes more negative). This increase in Seebeck coefficient displays distinctive behaviours in different spectral regions and is caused by the inclusion of Bi ions as foreign impurities. Furthermore, the Seebeck coefficients are used to determine the film electrical properties and enable, along with complementary characterisation including X-ray photoelectron spectroscopy, electronic band diagrams to be proposed for before and after Bi ion implantation. The photo-Seebeck technique is utilised for the first time to probe the trap states created due to the implantation, providing an understanding of the mechanisms behind non-equilibrium carrier-type reversal in an amorphous system, including the modification of electronic and optoelectronic properties such as the optical bandgap.

MIL-53(Al) forms uniform, 1D structures when produced from insoluble metal sources. Pyrolysis of these structures forms new alumina-based nanorods that extend up to 5 μm in one dimension. No external template or structure–direction is required.

Using adsorption isotherm data to determine heats of adsorption or predict mixture adsorption using the Ideal Adsorbed Solution Theory (IAST) relies on accurate fits of the data with continuous, mathematical models. Here, we derive an empirical two-parameter model to fit isotherm data of IUPAC types I, III, and V in a descriptive way based on the Bass model for innovation diffusion. We report 31 isotherm fits to existing literature data covering all six types of isotherms, various adsorbents, such as carbons, zeolites, and metal-organic frameworks (MOF), as well as different adsorbing gases (water, carbon dioxide, methane, nitrogen). We find several cases, especially for flexible MOFs, where previously reported isotherm models reached their limits and either failed to fit the data or could not sufficiently be fitted due to stepped type V isotherms. Moreover, in two instances models specifically developed for distinct systems are fitted with a higher R2 value compared to the models in the original reports. Using these fits, it is demonstrated how the new Bingel-Walton isotherm can be used to qualitatively assess the hydrophilic or hydrophobic behavior of porous materials from the relative magnitude of the two fitting parameters. The model can also be employed to find matching heats of adsorption values for systems with isotherm steps using one, continuous fit instead of partial, stepwise fits or interpolation. Additionally, using our single, continuous fit to model stepped isotherms in IAST mixture adsorption predictions leads to good agreement with results from the Osmotic Framework Adsorbed Solution Theory (OFAST) that was specifically developed for these systems using a stepwise, approximate fitting, yet is far more complex. Our new isotherm equation accomplishes all of these tasks with only two fitted parameters, providing a simple, accurate method for modeling a variety of adsorption behavior.

MYB plays a key role in gene regulation throughout the hematopoietic hierarchy and is critical for the maintenance of normal hematopoietic stem cells (HSC). Acquired genetic dysregulation of MYB is involved in the etiology of a number of leukemias, although inherited noncoding variants of the MYB gene are a susceptibility factor for many hematological conditions, including myeloproliferative neoplasms (MPN). The mechanisms that connect variations in MYB levels to disease predisposition, especially concerning age dependency in disease initiation, are completely unknown. Here, we describe a model of Myb insufficiency in mice that leads to MPN, myelodysplasia, and leukemia in later life, mirroring the age profile of equivalent human diseases. We show that this age dependency is intrinsic to HSC, involving a combination of an initial defective cellular state resulting from small effects on the expression of multiple genes and a progressive accumulation of further subtle changes. Similar to previous studies showing the importance of proteostasis in HSC maintenance, we observed altered proteasomal activity and elevated proliferation indicators, followed by elevated ribosome activity in young Myb-insufficient mice. We propose that these alterations combine to cause an imbalance in proteostasis, potentially creating a cellular milieu favoring disease initiation.

In many engineering scenarios, surface-active organic species are added to acidic solutions to inhibit the corrosion of metallic components. Given suitable selection, such corrosion inhibitors are highly effective, preventing significant degradation even in highly aggressive environments. Nevertheless, there are still considerable gaps in fundamental knowledge of corrosion inhibitor functionality, severely restricting rational development. Here, we demonstrate the capability of X-ray photoelectron spectroscopy (XPS), supported by ab initio modelling, for revealing key details of inhibited substrates. Attention is focussed on the corrosion inhibition of carbon steel through the addition of an exemplar imidazoline-based corrosion inhibitor (OMID) to aqueous solutions of both HCl and H2SO4. Most notably, it is demonstrated that interfacial chemistry varies with the identity of the acid. High resolution Fe 2p, O 1s, N 1s, and Cl 2p XPS spectra, acquired from well-inhibited carbon steel in 1 M HCl, show that there are two different singly protonated OMID species bound directly to the metallic carbon steel substrate. In sharp contrast, in 0.01 M H2SO4, OMID adsorbs onto an ultra-thin surface film, composed primarily of a ferric sulfate (Fe-2(SO4)(3))-like phase. Such insight is essential to efforts to develop a mechanistic description of corrosion inhibitor functionality, as well as knowledge-based identification of next generation corrosion inhibitors.

The separation of xylene isomers still remains an industrially challenging task. Here, porous purine-based metal-organic frameworks (MOFs) have been synthesized and studied for their potential in xylene separations. In particular, Zn(purine)I showed excellent

Perovskite solar cells (PSCs) based on organic-inorganic hybrid perovskites containing a small fraction of substituted alkali-metal cations have shown remarkable performance and stability. However, the role of these cations is unclear. The thermal- and moisture-induced degradation of FA1-xCsxPbI3 and (FA1-xCsx)1-yRbyPbI3 (where FA represents formamidinium, x, y = 0.1, 0.05) is investigated using in situ photoelectron spectroscopy (PES). Both compositions exhibit superior moisture stability compared with methylammonium lead iodide under 9 mbar of water vapor. Ga Kα hard X-ray PES is used to investigate the composition of the perovskites at depths up to 45 nm into the surface. This allows more accurate quantification of the alkali-metal distribution than is possible using conventional X-ray PES. The addition of RbI results in a fairly homogeneous distribution of both Cs+ and Rb+ in the surface layers (in contrast to surface Cs depletion seen in its absence), together with a marked reduction in surface iodide vacancies. Overall, RbI is found to play a critical role in increasing the thermal stability of FA1-xCsxPbI3 by providing a source of I- that fills iodine vacancy sites in the perovskite lattice, while Rb+ is not substantially incorporated into the perovskite. We suggest that the concomitant increase in ion migration barriers in the surface layers is key to improved PSC performance and long-lasting stability.

Purpose This paper aims to provide a brief and accessible introduction to genetics and epigenetics for forensic practitioners. It provides two primers which define key genetic concepts and explain what epigenetic mechanisms actually are. The primers are provided alongside sections that focus on genetic research relevant to forensic practice, with a range of key messages that support the call to contextualise harmful behaviour and build better awareness of gene-environment relationships. Design/methodology/approach This is an opinion paper. Findings Select and seminal studies from the genetic literature that have forensic practice relevance are cited. These include studies from candidate gene research and epigenetic research. They highlight a number of key themes, including the way neurodevelopment and behaviour are contextually adjusted to fit certain environments, with epigenetic changes being an underpinning biological mechanism that facilitates this. Research limitations/implications This article aims to introduce forensic practitioners to basic concepts in genetics and epigenetics so that they are able to engage with the relevant literature and understand the far-reaching implications for forensic practice. Practical implications It is becoming increasingly useful for forensic practitioners to appreciate how life experiences are encoded into biology through epigenetics. This paper highlights the potential of genetic and epigenetic research to provide major contributions to real-world practice in the coming years. It provides a modern biopsychosocial perspective on harmful behaviour and helps deepen the understanding of our efforts to support behaviour change. It offers ways to think of social and rehabilitative initiatives in biological terms. Originality/value This paper is one of few modern texts that focusses on the relevance of genetic and epigenetic research in applied forensic practice. It aims to introduce relevant concepts in an accessible manor. It intends to introduce biologically informed ways of understanding harmful behaviour within context and with attention to its function. It contributes to a de-pathologising narrative.

The development of intrinsically safe and environmentally sustainable energy storage devices is a significant challenge. Recent advances in aqueous rechargeable lithium-ion batteries (ARLIBs) have made considerable steps in this direction. In parallel to the ongoing progress in the design of aqueous electrolytes that expand the electrochemically-stable potential window, the design of negative electrode materials exhibiting large capacity and low intercalation potential attracts great research interest. Herein, we report the synthesis of high purity nanoscale Chevrel Phase (CP) Mo6S8 via a simple, efficient and controllable molecular precursor approach with significantly decreased energy consumption compared to the conventional approaches. Physical characterization of the obtained product confirms the successful formation of CP-Mo6S8 and reveals its crystal structure in the nanoscale range. Due to their unique structural characteristics, the Mo6S8 nanocubes exhibit fast kinetics in a 21 m lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte as a result of the shorter Li+ ion diffusion distance. Full battery cells comprised of Mo6S8 and LiMn2O4 as negative and positive electrode materials, respectively, operate at 2.23 V delivering a high energy density of 85 Wh/kg (calculated on the total mass of active materials) under 0.2 C-rate. At 4 C, the Coulombic efficiency (CE) is determined to be 99% increasing to near 100% at certain cycles. Post-mortem physical characterization demonstrates that the Mo6S8 anode maintained its crystallinity, thereby exhibiting outstanding cycling stability. The cell outperforms the commonly used vanadium-based (VO2 (B), V2O5) or (NASICON)-type LiTi2(PO4)3 anodes, highlighting the promising character of the nanoscale CP-Mo6S8 as a highly efficient anode material. In summary, the proposed synthetic strategy is expected to stimulate novel research towards the widespread application of CP-based materials in various aqueous and non-aqueous energy storage systems.

A general procedure has been developed for synthesizing four MOFs sharing similar chains of AlO6 octahedra (CAU-10, NOTT-300, MIL-53-TDC, and MIL-160). CAU-10 has been synthesized with eight differently substituted ligands to impart different characteristics into the pore space. Isotherms of CO2, CH4, and N2 were measured on all MOFs synthesized in this work to assess the effects of functional group and surface area on adsorption behavior. At low pressure (100 mbar), structures incorporating polar functional groups have the highest adsorption of CO2, while the structures with the highest surface areas have the highest adsorption of CO2 at higher pressure (1000 mbar). The heterocyclic and amine-substituted structures show the greatest CO2 adsorption and Henry’s law selectivity among all CAU-10 structures in this work. Comparison of CAU-10 MOFs substituted with a nitro group at different positions on the ligand (carbon 4 vs 5) showed that positioning the nitro group at the side of the pore rather than the center resulted in increased loading of all adsorbates over the studied pressure range up to 1 bar.

Information on mixture adsorption equilibrium is vital in developing adsorption-based separation processes. Because measuring mixture adsorption is more difficult than measuring single-component ad...

Owing to their highly tunable structures, metal–organic frameworks (MOFs) are considered suitable candidates for a range of applications, including adsorption, separation, sensing and catalysis. However, MOFs must be stable in water vapour to be considered industrially viable. It is currently challenging to predict water stability in MOFs; experiments involve time-intensive MOF synthesis, while modelling techniques do not reliably capture the water stability behaviour. Here, we build a machine learning-based model to accurately and instantly classify MOFs as stable or unstable depending on the target application, or the amount of water exposed. The model is trained using an empirically measured dataset of water stabilities for over 200 MOFs, and uses a comprehensive set of chemical features capturing information about their constituent metal node, organic ligand and metal–ligand molar ratios. In addition to screening stable MOF candidates for future experiments, the trained models were used to extract a number of simple water stability trends in MOFs. This approach is general and can also be used to screen MOFs for other design criteria. Metal–organic frameworks (MOFs) are attractive materials for gas capture, separation, sensing and catalysis. Determining their water stability is important, but time-intensive. Batra et al. use machine learning to screen water-stable MOFs and identify chemical features supporting their stability.

Supported bimetallic nanoparticles (BNPs) are promising catalysts, but study on their compositional and structural changes under reaction conditions remains a challenge. In this work, the structure of PtNi BNPs supported on UiO-67 metal–organic framework (MOF) catalyst (i.e., PtNi@UiO-67) was investigated by in situ by near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). The results showed differences in the reduction behaviour of Ni species in PtNi BNPs and monometallic Ni supported on UiO-67 catalysts (i.e., PtNi@UiO-67 and Ni@UiO-67), suggesting charge transfer between metallic Pt and Ni oxides in PtNi@UiO-67. Under CO oxidation conditions, Ni oxides segregated to the outer surface of the BNPs forming a thin layer of NiOx on top of the metallic Pt (i.e., a NiOx-on-Pt structure). This resulted in a core-shell structure which was confirmed by high-resolution scanning transmission electron microscopy (HR-STEM). Accordingly, the layer of NiOx on PtNi BNPs, which is stabilised by charge transfer from metallic Pt, was proposed as the possible active phase for CO oxidation, being responsible for the enhanced catalytic activity observed in the bimetallic PtNi@UiO-67 catalyst.

Adsorption of corrosive SO2 gas occurs in metal-organic frameworks (MOFs) including UiO-66. Improvements in SO2 capacity is obtained through the incorporation of residual modulators in the UiO-66 f...

A mixed linker strategy has led to the discovery of the new metal–organic framework material, GT-18 (GT = Georgia Tech), which has no open metal sites and a chiral structure. The material includes ...

The structure of aluminum carbide (from two different manufacturers) has been interrogated by 27Al solid-state NMR in an effort to accurately characterize the material. Quadrupolar lineshapes for 2...

An in-depth study on post-synthetic modification of residual metal in carbide-derived carbons (CDCs) from an Al4C3 starting material has been performed. Ambient temperature high humidity studies reveal the conversion of residual parent nanoparticles to poly(aluminum chloride) (PAC). Alkaline modification was employed resulting in the formation of amorphous Al(OH)3 nanoparticles within 24 h of reaction. After aging for up to 11 days, amorphous nanoparticles convert to well-crystallized α-Al(OH)3 (bayerite). Al4C3-CDCs with amorphous Al(OH)3 display significantly-enhanced interactions with SO2 and CO2 while X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance infrared (ATR-IR) spectroscopy indicated no significant change in the surface chemistry of the carbon. SO2 breakthrough results at 1000 ppm SO2 exhibit uptakes near 2 mmol g−1, displaying viability for these adsorbents in flue gas remediation applications. The results of this work provide detailed modification strategies for tuning the extent and type of residual metal embedded in the final CDC structure, along with further insights into the ramifications of oxygen functionalities and pore size distribution of CDCs for SO2 adsorption.

CO2 hydrogenation with renewable energy is one of the promising approaches to mitigate CO2 emissions and produce sustainable chemicals and fuels. The effect of adding H2O in the feed gas on the activity and selectivity of In2O3/ZrO2 catalysts for CO2 hydrogenation to methanol was studied using combined experimentatal and computational efforts. Notably, adding an appropriate amount of H2O (0.1 mol%) in the feed gas significantly enhanced the CH3OH formation (ca. 20%) with improved selectivity. Characterization with STEM/EDS and CO2-TPD confirmed the preservation of In-Zr strong interaction in the presence of additional H2O and H2O-induced oxygen vacancies, which significantly improved CO2 adsorption capacity. XPS analysis revealed the formation of InOOH species due to H2O addition, which appeared to correlate to H2O-dependant enhancement of CH3OH formation. Density functional theory calculations rationalized the effect of surface H2O on InOOH formation and its correlation to CH3OH synthesis activity. Adding H2O was found to facilitate surface InOOH formation, suppress CO formation through COOH* intermediate, and promote CH3OH formation via HCOO* intermediate. However, excess H2O addition resulted in aggregation of In species and reduction of surface In0 for H2 dissociation.

This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (NanoMOFdeli), ERC-2016-COG 726380, Innovate UK (104384) and EPSRC IAA (IAA/RG85685). N.R. acknowledges the support of the Cambridge International Scholarship and the TrinityHenry Barlow Scholarship (Honorary). O.K.F. and R.Q.S. acknowledge funding from the U.S. Department of Energy (DE-FG02-08ER15967). R.S.F. and D.B. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (SCoTMOF), ERC-2015-StG 677289. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525. The authors gratefully acknowledge funding from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, through the Hydrogen Storage Materials Advanced Research Consortium (HyMARC). This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. J.D.E. acknowledges the support of the Alexander von Humboldt Foundation and the Center for Information Services and High Performance Computing (ZIH) at TU Dresden. S.K.G. and S.M. acknowledge SERB (Project No. CRG/2019/000906), India for financial support. K.K. and R.K. acknowledge Active Co. Research Grant for funding. S.K. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (COSMOS), ERC-2017-StG 756489. N.L. and J.G.M acknowledge funding from the European Commission through the H2020-MSCA-RISE-2019 program (ZEOBIOCHEM -872102) and the Spanish MICINN and AEI/FEDER (RTI2018-099504-B-C21). N.L. thanks the University of Alicante for funding (UATALENTO17-05). ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706) S.M.J.R. and A.L. wish to thank the Fund for Scientific Research Flanders (FWO), under grant nos. 12T3519N and 11D2220N. L.S. was supported by the EPSRC Cambridge NanoDTC EP/L015978/1. C.T.Y. and T.S.N. acknowledges funds from the National Research Foundation of Korea, NRF-2017M3A7B4042140 and NRF-2017M3A7B4042235. P.F. and H. Y. acknowledge US Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Award No. DE-SC0010596 (P.F.). R.O. would like to acknowledge funding support during his Ph.D. study from Indonesian Endowment Fund for Education-LPDP with the contract No. 202002220216006. Daniel Siderius: Official contribution of the National Institute of Standards and Technology (NIST), not subject to copyright in the United States of America. Daniel Siderius: Certain commercially available items may be identified in this paper. This identification does not imply recommendation by NIST, nor does it imply that it is the best available for the purposes described. B.V.L, S.T.E and A.M.P acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Program (Grant agreement no. 639233, COFLeaf)., Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of microand mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This roundrobin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible., European Research Council (ERC) ERC-2016-COG 726380 ERC-2015-StG 677289 ERC-2017-StG 756489 639233, UK Research & Innovation (UKRI) Innovate UK 104384 UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) IAA/RG85685, Cambridge International Scholarship TrinityHenry Barlow Scholarship, United States Department of Energy (DOE) DE-FG02-08ER15967, National Nuclear Security Administration DE-NA-0003525, United States Department of Energy (DOE), Alexander von Humboldt Foundation, Center for Information Services and High Performance Computing (ZIH) at TU Dresden, Department of Science & Technology (India), Science Engineering Research Board (SERB), India CRG/2019/000906, Active Co. Research Grant, European Commission through the H2020-MSCA-RISE-2019 program ZEOBIOCHEM -872102, Spanish MICINN and AEI/FEDER RTI2018-099504-B-C21, University of Alicante UATALENTO17-05, Spanish Government SEV-2017-0706 FWO 12T3519N 11D2220N, UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) EP/L015978/1, National Research Foundation of Korea NRF-2017M3A7B4042140 NRF-2017M3A7B4042235, United States Department of Energy (DOE) DE-SC0010596, Indonesian Endowment Fund for Education-LPDP 202002220216006

In this work, the degradation of the metal-organic framework (MOF) DMOF-1 as a function of water adsorption was investigated. As the quantity of water vapor adsorbed by DMOF-1 increases, degradation of the MOF from hydrolysis accelerates. Degradation was attributed to clustering of water molecules in the void space of DMOF-1, as seen in

Conductometric gas sensors (CGS) provide a reproducible gas response at a low cost but their operation mechanisms are still not fully understood. In this paper, we elucidate the nature of interactions between SnO2, a common gas-sensitive material, and O2, a ubiquitous gas central to the detection mechanisms of CGS. Using synchrotron radiation, we investigated a working SnO2 sensor under operando conditions via near-ambient pressure (NAP) XPS with simultaneous resistance measurements, and created a depth profile of the variable near-surface stoichiometry of SnO2−x as a function of O2 pressure. Our results reveal a correlation between the dynamically changing surface oxygen vacancies and the resistance response in SnO2-based CGS. While oxygen adsorbates were observed in this study we conclude that these are an intermediary in oxygen transport between the gas phase and the lattice, and that surface oxygen vacancies, not the observed oxygen adsorbates, are central to response generation in SnO2-based gas sensors.

Conductometric gas sensors (CGS) provide a reproducible gas response at a low cost but their operation mechanisms are still not fully understood. In this paper, we elucidate the nature of interactions between SnO

Graphene nanobubbles (GNBs) are formed from matter trapped between a two-dimensional material and a substrate. Such structures exhibit a wide range of new fundamental phenomena and are promising for nanoelectronic applications. However, a central part of the synthesis methods leads to the formation of GNBs with undetermined matter composition. Moreover, none of the GNBs’ synthesis methods allow one to control the type of trapped matter. In a recent paper [K.M. Zahra, PCCP, 22,7606 (2020)], the authors proposed a new approach that allows the production of GNBs on a copper substrate with pure nitrogen inside in a controlled manner. In this work, we continue this research by studying the geometry of the GNBs in detail and indirectly measuring the internal pressure, which depends on the van der Waals adhesion energy and elastic properties of the graphene membrane. In agreement with other studies, we observe that dome-shaped bubbles exhibituniversal scaling law, i.e., constant height to radius ratio. However, the measured height to radius ratio differs significantly from the known results of experiments and computer simulations. This deviation is explained by applying the membrane theory and taking into account the high adhesion of the copper substrate and graphene sheet. The adhesion energy calculated based on experimental data is close to the measurements performed by other experimental techniques.

To evaluate the long-term incidence of structural valve deterioration (SVD) in patients who underwent transcatheter aortic valve implantation (TAVI).Between 2008 and 2018, 693 underwent TAVI at two centres. Four hundred and twenty-one (421) patients (mean age 83.6±6.0 yrs) survived for ≥2 years post TAVI and had at least two consecutive transthoracic echocardiographies (TTEs) with the latest TTE no less than 2 years after TAVI, and were therefore included in the analysis for SVD. Median follow-up was 4.7 (3.6-6.0) years and median echocardiography follow-up 3 (3.0-4.0) years. All-cause mortality was 30.9% (130) with a median time to death of 4.1 (3.0-5.6) years. The cumulative incidence of SVD increased from 1.7% (95% CI, 0.4-2.9) at 3 years to 3.5% (95% CI, 1.5-5.8) at 5 years and 4.7% (95% CI, 1.6-7.9) at 10 years. The overall median time to SVD was 3 (2-4) years. Twelve (12) patients demonstrated SVD stage 2, and 1 patient stage 3. No SVD required re-intervention. All other patients showed no significant changes in valve parameters over time.Structural valve deterioration is an uncommon event, occurring in 5% over a total follow-up of 10 years. Most patients show stable valve parameters. However, the analysis is limited by the loss of follow-up (owing to patient mortality), which renders extrapolation of the data to a younger patient population difficult.

Background: Renal denervation has been shown to lower blood pressure in the presence of antihypertensive medications; however, long-term safety and efficacy data from randomised trials of renal denervation are lacking. In this pre-specified analysis of the SPYRAL HTN-ON MED study, we compared changes in blood pressure, antihypertensive drug use, and safety up to 36 months in renal denervation versus a sham control group. Methods: This randomised, single-blind, sham-controlled trial enrolled patients from 25 clinical centres in the USA, Germany, Japan, the UK, Australia, Austria, and Greece, with uncontrolled hypertension and office systolic blood pressure between 150 mm Hg and 180 mm Hg and diastolic blood pressure of 90 mm Hg or higher. Eligible patients had to have 24-h ambulatory systolic blood pressure between 140 mm Hg and less than 170 mm Hg, while taking one to three antihypertensive drugs with stable doses for at least 6 weeks. Patients underwent renal angiography and were randomly assigned (1:1) to radiofrequency renal denervation or a sham control procedure. Patients and physicians were unmasked after 12-month follow-up and sham control patients could cross over after 12-month follow-up completion. The primary endpoint was the treatment difference in mean 24-h systolic blood pressure at 6 months between the renal denervation group and the sham control group. Statistical analyses were done on the intention-to-treat population. Long-term efficacy was assessed using ambulatory and office blood pressure measurements up to 36 months. Drug surveillance was used to assess medication use. Safety events were assessed up to 36 months. This trial is registered with ClinicalTrials.gov, NCT02439775; prospectively, an additional 260 patients are currently being randomly assigned as part of the SPYRAL HTN-ON MED Expansion trial. Findings: Between July 22, 2015, and June 14, 2017, among 467 enrolled patients, 80 patients fulfilled the qualifying criteria and were randomly assigned to undergo renal denervation (n=38) or a sham control procedure (n=42). Mean ambulatory systolic and diastolic blood pressure were significantly reduced from baseline in the renal denervation group, and were significantly lower than the sham control group at 24 and 36 months, despite a similar treatment intensity of antihypertensive drugs. The medication burden at 36 months was 2·13 medications (SD 1·15) in the renal denervation group and 2·55 medications (2·19) in the sham control group (p=0·26). 24 (77%) of 31 patients in the renal denervation group and 25 (93%) of 27 patients in the sham control group adhered to medication at 36 months. At 36 months, the ambulatory systolic blood pressure reduction was −18·7 mm Hg (SD 12·4) for the renal denervation group (n=30) and −8·6 mm Hg (14·6) for the sham control group (n=32; adjusted treatment difference −10·0 mm Hg, 95% CI −16·6 to −3·3; p=0·0039). Treatment differences between the renal denervation group and sham control group at 36 months were −5·9 mm Hg (95% CI −10·1 to −1·8; p=0·0055) for mean ambulatory diastolic blood pressure, −11·0 mm Hg (−19·8 to −2·1; p=0·016) for morning systolic blood pressure, and −11·8 mm Hg (−19·0 to −4·7; p=0·0017) for night-time systolic blood pressure. There were no short-term or long-term safety issues associated with renal denervation. Interpretation: Radiofrequency renal denervation compared with sham control produced a clinically meaningful and lasting blood pressure reduction up to 36 months of follow-up, independent of concomitant antihypertensive medications and without major safety events. Renal denervation could provide an adjunctive treatment modality in the management of patients with hypertension. Funding: Medtronic. © 2022 Elsevier Ltd

In recent times, mixed-cation metal halide perovskites have shown promising photovoltaic performance, and the long-term stability of these metal halide perovskites has also been considerably improved by incorporating additives into the perovskite precursor. Here, the role of ionic liquid additives in improving the stability of perovskite is investigated by in-situ surface sensitive studies. A small amount (0.3mol %) of 1-octyl-3-methylimidazolium chloride ionic liquid (IL) is incorporated into FA0.9Cs0.1PbI3 (FACs) (where FA represents the formamidinium cation, CH=(NH2)2 +). The thermal- and moisture-induced decomposition of FACs and IL-FACs is investigated using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). A comparative study of the pristine and IL-incorporated FACs compositions shows that the IL additive prevents the out-diffusion of organic ion (FA+) from the lattice for temperatures up to 100 °C under 9 mbar water vapour and up to 150 °C under UHV conditions. Both compositions exhibit better stability under 9 mbar water vapour (equivalent to ~30% relative humidity) compared with conventional methylammonium lead iodide (MAPbI3). The champion device fabricated with IL additive exhibits an improved power conversion efficiency (PCE) of 16% compared with the 13% PCE of the pristine FACs sample. Overall, the results suggest that the IL additive acts to improve the device performance as well as the stability of perovskites under thermal annealing in dry environments, but that a careful choice of IL will be necessary for full passivation in wet environments.

Purpose: To review information pertaining to secondary glaucoma following infant lensectomy and provide evidence to support the mechanism responsible for this condition. Methods: Reported risk factors and proposed mechanisms for infantile aphakic glaucoma are reviewed. Laboratory studies and clinical observations in affected patients with glaucoma are described. Evidence of postoperative anterior chamber fibrosis is reviewed and interpreted. Results: Clinical evidence demonstrated the development of anterior chamber fibrosis following infant cataract surgery. Laboratory studies showed liberated lens epithelial cell transition to fibroblasts. Conclusions: The review and assessment of laboratory and clinical evidence support the proposal that infantile aphakic glaucoma is caused, in part, by postoperative anterior chamber fibroization related to lens cell dispersion, cytokine activation, and epithelial-mesenchymal transition with resultant filtration angle fibrosis and secondary loss of filtration function. [ J Pediatr Ophthalmol Strabismus . 2022;59(4):236–242.]

Developing a simple, safe, and efficient route for the preparation of nanoparticulate ternary Chevrel phases MxMo6S8 (CPs; where M = metal) is of great interest because of their applications in energy conversion and storage technologies. Currently, the wide use of these materials is restricted by the prolonged reaction time, the high energy demands required for their synthesis, the complexity of the preparation process, and the ambiguity in the size of the resultant particles. Herein, we report a simple, efficient, and controllable molecular precursor approach for the synthesis of nanoscale CPs without the use of hydrogen gas as a reducing agent. A mixture of precursors based on molybdenum and copper dithiocarbamate complexes was subjected to thermolysis in the presence of finely divided molybdenum to furnish the copper CP, Cu2Mo6S8. The successful formation of the Cu2Mo6S8 CP is confirmed by X-ray diffraction analysis and Raman spectroscopy, while the surface chemistry of the material was examined by X-ray photoelectron spectroscopy photon depth profiling via tunable synchrotron radiation. Microscopic characterization results demonstrate that the synthesized material has a homogeneous structure at the nanoscale, in contrast to the microparticles obtained from conventional approaches previously reported. The prepared CP was assessed as an electrocatalyst for the hydrogen evolution reaction in acidic media. Because of its unique nanoscale texturing, the Cu-leached CP, Mo6S8, exhibits a highly promising electrocatalytic activity toward hydrogen evolution with an overpotential required to reach a current density of 10 mA cm-2 equal to 265 mV versus reversible hydrogen electrode. The overpotential reduces to 232 mV upon mixing of the catalyst with 20% w/w of high-conductivity carbon. It is expected that the proposed synthetic strategy, which represents a facile route to tailored CPs, can be extended to the preparation of versatile, easily tunable CP Mo6S8-based electrode materials for applications in electrocatalysis.

Vibrational modes of chemical bonds in organic erbium (Er