A new, facile, general one-phase synthesis for thiol-functionalized gold, palladium, and iridium nanoparticles, using tetrahydrofuran (THF) as the solvent and lithium triethylborohydride (Superhydride) as the reducing agent, is presented. For octadecanethiol-functionalized gold (Au/ODT) nanoparticles, HRTEM of drop-cast particle-films revealed the formation of spherical particles of d = 4 ± 0.3 nm average size. Electron diffraction shows fcc packing arrangement, similar to that of bulk gold. The crystalline gold cores are surrounded with closely packed n-alkyl chains mainly in an all-trans conformation, adopting orthorhombic packing as confirmed by FTIR spectroscopy. Particles are arranged in a discrete solidlike assembly with a correlation length of ∼5 nm, as the interparticle distance (center-to-center) and a constant edge-to-edge distance of 1 nm as shown by FFT analysis. Using the same synthetic procedure gold nanoparticles functionalized with 11-hydroxyundecane-1-thiol and with 4‘-bromo-4-mercaptobiphenyl were prepared. TEM images of drop-cast Pd/ODT and Ir/ODT nanoparticles show an average size of 2.25 nm for the former, while for the latter the distribution is broader with the majority of particles between 2.25 and 4.25 nm. Both nanoparticles are crystalline with fcc packing. FTIR spectroscopy reveals that octadecyl chains are close-packed in all-trans conformation, and that there is presumably one chain in unit cell.

We have functionalized amorphous Fe2O3 nanoparticles with alkanesulfonic and octadecanephosphonic acids. TEM reveals nanoparticles 5−10 nm in diameter. FTIR spectra suggest that while in all cases the alkyl chains are packed in a solid-like arrangement, packing disorder increased with decreasing chain length. TGA of the sulfonic acid-functionalized Fe2O3 nanoparticles shows that moieties started to decompose and desorb from the iron oxide surface at about 260 °C. In the case of the octadecanephosphonic acid (OPA)-functionalized Fe2O3, moieties started to decompose and desorb at 340 °C. It is suggested that free Fe−OH groups can serve as proton donors to assist in the sulfonic acid desorption process and that because of the diprotic nature of the phosphonic acid these free surface Fe−OH groups may no longer be available. Among all, the octadecanesulfonic acid coating displays the lowest magnetization, which may be explained by the high packing and ordering of the alkyl chains on the particle surface. The saturation curve of the OPA case gives the smallest value of magnetization we have ever measured for functionalized Fe2O3 nanoparticles. It is suggested that the spin state of surface Fe3+ ions is affected by the bonded surfactant, through a mechanism of pπ−dπ P−O, and dπ−dπ Fe−P interactions and that the phosphonate empty d orbitals increase magnetic interactions between neighboring Fe3+ spins.

Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytical methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world’s rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals.

The surface-induced ordering in thin films of asymmetric deuterated polystyrene (dPS)-poly(viny1pyridine) (PVP) diblock and triblock copolymers of comparable polymerization index and PVP volume fraction -0.25) was studied using transmission electron microscopy, atomic force microscopy, secondary ion massspectrometry, and neutron reflectivity. The morphology of both di-and triblock copolymer films was found to be cylindrical except for the layer adjacent to the silicon oxide surface, which due to the strong interaction of silica with PVP, was lamellar. The spacing between adjacent cylindrical layers was found to be consistent with mean field theory predictions. In the triblock copolymer films the cylindrical layers were oriented parallel to the silicon oxide surface, and no decay of the ordered structure was observed for at least 12 periods. If the total film thickness t' deviated from t = [ ( n + 0.711210 + 1821 A, where n is an integer, islands or holes formed at the vacuum interface. The height of the holes or islands reached its equilibrium value, 210 A, after annealing 24 hat 180 O C . In contrast, it was far more difficult to orient parallel to the silicon oxide surface the microphase-separated cylindrical domains in the diblock copolymer films. As a result no islands or holes were observed even after annealing for 5 days at 180 O C . We concluded that the difference in ordering behavior was due to the ability of the triblock copolymer to form an interconnected micelle network while the diblock copolymer formed domains that were free to move with respect to each other. This conclusion was further confirmed by diffusion measurements which showed that the PS homopolymer penetrated easily into the ordered diblock copolymer films and was excluded from the ordered triblock copolymer films.

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IV.

Background We aimed to assess the efficacy and safety of two neutralising monoclonal antibody therapies (sotrovimab [Vir Biotechnology and GlaxoSmithKline] and BRII-196 plus BRII-198 [Brii Biosciences]) for adults admitted to hospital for COVID-19 (hereafter referred to as hospitalised) with COVID-19. Methods In this multinational, double-blind, randomised, placebo-controlled, clinical trial (Therapeutics for Inpatients with COVID-19 [TICO]), adults (aged ≥18 years) hospitalised with COVID-19 at 43 hospitals in the USA, Denmark, Switzerland, and Poland were recruited. Patients were eligible if they had laboratory-confirmed SARS-CoV-2 infection and COVID-19 symptoms for up to 12 days. Using a web-based application, participants were randomly assigned (2:1:2:1), stratified by trial site pharmacy, to sotrovimab 500 mg, matching placebo for sotrovimab, BRII-196 1000 mg plus BRII-198 1000 mg, or matching placebo for BRII-196 plus BRII-198, in addition to standard of care. Each study product was administered as a single dose given intravenously over 60 min. The concurrent placebo groups were pooled for analyses. The primary outcome was time to sustained clinical recovery, defined as discharge from the hospital to home and remaining at home for 14 consecutive days, up to day 90 after randomisation. Interim futility analyses were based on two seven-category ordinal outcome scales on day 5 that measured pulmonary status and extrapulmonary complications of COVID-19. The safety outcome was a composite of death, serious adverse events, incident organ failure, and serious coinfection up to day 90 after randomisation. Efficacy and safety outcomes were assessed in the modified intention-to-treat population, defined as all patients randomly assigned to treatment who started the study infusion. This study is registered with ClinicalTrials.gov , NCT04501978 . Findings Between Dec 16, 2020, and March 1, 2021, 546 patients were enrolled and randomly assigned to sotrovimab (n=184), BRII-196 plus BRII-198 (n=183), or placebo (n=179), of whom 536 received part or all of their assigned study drug (sotrovimab n=182, BRII-196 plus BRII-198 n=176, or placebo n=178; median age of 60 years [IQR 50–72], 228 [43%] patients were female and 308 [57%] were male). At this point, enrolment was halted on the basis of the interim futility analysis. At day 5, neither the sotrovimab group nor the BRII-196 plus BRII-198 group had significantly higher odds of more favourable outcomes than the placebo group on either the pulmonary scale (adjusted odds ratio sotrovimab 1·07 [95% CI 0·74–1·56]; BRII-196 plus BRII-198 0·98 [95% CI 0·67–1·43]) or the pulmonary-plus complications scale (sotrovimab 1·08 [0·74–1·58]; BRII-196 plus BRII-198 1·00 [0·68–1·46]). By day 90, sustained clinical recovery was seen in 151 (85%) patients in the placebo group compared with 160 (88%) in the sotrovimab group (adjusted rate ratio 1·12 [95% CI 0·91–...