The selective oxidation of bioderived molecules by gold catalysts

The selective oxidations of the bioderived molecules, 1,2-propanediol, 1,3-propanediol and glycerol, were investigated using gold based catalysts. These reactions were carried out in both low pressure glass reactors and high pressure autoclaves. The reaction conditions such as temperature and amount of base were investigated to order to achieve the optimum conditions. The gold based catalysts used were prepared by sol immobilisation and impregnation methods. The supports tested were activated carbon, titania, ceria and magnesium oxide. The ceria supported catalyst was demonstrated to be extremely selective for the oxidation of 1,2-propanediol in methanol in which methyl lactate is the desired product. The addition of palladium to the gold catalyst led to an increase in activity for all supports, however, in the case of the ceria supported catalyst a decrease in selectivity was observed. The use of a magnesium oxide support was found to be advantageous in the oxidation of 1,3-propanediol and model compounds 1,4-propanediol and butyrolactone. An increase in activity and selectivity to the desired products, dimethyl malonate and dimethyl succinate, was demonstrated when this catalyst support was used. The structure of the support was found to be Mg(OH)2 when the catalyst was prepared by sol immobilisation. When prepared by impregnation methods the support retained its periclase MgO structure but was found to be far less selective than the Mg(OH)2 support.The use of this support for the oxidation of glycerol was investigated. When gold is alloyed with platinum on this support it is possible to achieve high conversions of glycerol and good selectivities to glyceric acid in base free condition

The role of Mg(OH)2 in the so-called 'base-free' oxidation of glycerol with AuPd catalysts

Mg(OH)2 and Mg(OH)2 containing materials can provide excellent performance as supports for AuPd nanoparticles for oxidation of glycerol in the absence of base, which is considered to be a result of additional basic sites on the support's surface. However, its influence on the reaction solution is not generally discussed. In this paper, we examine, in detail, the relationship between the basic Mg(OH)2 support and AuPd nanoparticles using four types of catalyst, where the physical interaction between Mg(OH)2 and AuPd was adjusted. It was found that the activity of the AuPd nanoparticles increased with the amount of Mg(OH)2 added under base-free conditions, regardless of its interaction with the noble metals. In order to investigate how Mg(OH)2 affected glycerol oxidation, detailed information about the performance of AuPd/Mg(OH)2, physically mixed (AuPd/C+Mg(OH)2) and (AuPd/C+NaHCO3) was obtained and compared. Furthermore, NaOH and Mg(OH)2 were added during the reaction using AuPd/C. All these results indicate that the distinctive and outstanding performance of Mg(OH)2 supported catalysts in base-free condition is in fact directly related to its ability to affect the pH during the reaction and as such, assists with the initial activation of the primary alcohol which is considered to be the rate determining step in the reactionperformance of Mg(OH)2 supported catalysts in base-free condition could be correlated to its ability to affect the pH during the reaction

A micropacked-bed multi-reactor system with in situ raman analysis for catalyst evaluation

AbstractA micropacked-bed multi-reactor platform with integrated portable Raman spectrometer is presented for fast evaluation of catalyst activity and stability for gas/liquid/solid reactions. The silicon-glass microreactor was designed and fabricated so that pockets containing the liquid reaction mixture were created after each packed bed, into which the laser could be directed for Raman spectral acquisition. Using the oxidation of benzyl alcohol as a model reaction, the Raman spectrum was found to be affected both by temperature and by the composition of the multiphase reaction mixture which was related to the reaction conversion. These effects were accounted for by calibrating the Raman spectra at the reaction temperature using mixtures produced by the reactors that were analysed independently by gas chromatography. Fourteen catalysts containing different combinations of Au, Pd and Pt supported on TiO2 prepared by sol-immobilisation (SI) and standard impregnation (SImp) techniques were tested. The results showed that the activity of the catalysts prepared by SI was overall higher than those prepared by SImp, while the activity sequence followed the same pattern: Pd>AuPd>AuPdPt>PdPt>(Au, Pt, AuPt). The Pd and AuPd catalysts from both SI and SImp were stable in 5-h testing, however, for the PdPt and AuPdPt catalysts prepared by SI deactivation was observed

Solvent inhibition in the liquid-phase catalytic oxidation of 1,4-butanediol: understanding the catalyst behaviour from NMR relaxation time measurements

Catalytic reaction studies and Nuclear Magnetic Resonance (NMR) relaxation time measurements have been compared to study the influence of competitive adsorption of reactant and solvent on catalytic conversion. The reaction chosen is the aerobic catalytic oxidation of 1,4-butanediol in methanol over different supported-metal catalysts. From the NMR T1/T2 ratio, where T1 is the longitudinal and T2 the transverse spin relaxation time, the relative affinity of reactant and solvent for different catalytic surfaces is determined. The catalysts with the lowest activity show a preferential surface affinity for the solvent compared to the reactant. Conversely, the catalyst with the highest activity shows a preferential surface affinity for the reactant compared to the solvent. Significantly, Ru/SiO2, which is totally inactive for the oxidation of 1,4-butanediol, exhibited a lower T1/T2 ratio (surface affinity) for 1,4-butanediol (reactant) than for a “weakly-interacting” alkane, indicating a very poor surface affinity for the diol functionality. The results provide direct evidence of the importance of the adsorbate-adsorbent interactions on catalyst activity in liquid-phase oxidations and indicate that the competitive adsorption of the solvent plays an important role in these reactions. This work demonstrates that NMR relaxation time analysis is a powerful method for comparing adsorption of liquids in porous catalysts, providing valuable information on the affinity of different chemical species for a catalyst surface. Moreover, the results demonstrate that NMR relaxation time measurements can be used not only to guide selection of solvent for use with a specific catalyst, but also selection of the catalyst itself. The results suggest that this method may be used to predict catalyst behaviour, enabling improved design and optimisation of heterogeneous catalytic processes

Inter-connected and open pore hierarchical TS-1 with controlled framework titanium for catalytic cyclohexene epoxidation

A post-synthesis method was developed to reduce the extra-framework titanium (Ti) in TS-1 zeolites (Si/Ti ratio = 50), in which tetrapropylamonium hydroxide (TPAOH) aqueous solution was used to promote the dissolution, redistribution and recrystallization processes, and hence to convert amorphous Ti species into zeolitic phases. It was found that TPAOH could effectively convert the extra-framework Ti into framework Ti, and the TPAOH concentration influenced the pore structure significantly. Under lower TPAOH concentration (i.e. 0.05–0.4 M), only closed meso-/macropores (grooves and hollow cavities) can be created in the TS-1 crystals. At an optimum concentration of 0.5 M TPAOH, open and connected hierarchical mesopores and macropores were created in the resulting TS-1 zeolites. Compared with the parent TS-1, the amount of extra-framework titanium was reduced significantly from 14.4% to 0.3% and the meso-/macropore volume was increased from 0.014 to 0.168 cm3 g−1 accordingly upon TPAOH post treatment. Along with the parent TS-1 zeolite, the developed hierarchical TS-1 zeolites were assessed in the catalytic epoxidation of cyclohexene. It was confirmed that the amount of framework titanium and hierarchical pore structure influenced the catalytic activity considerably. Closed porosity slightly improved the cyclohexene conversion, whereas the open-pore sample shows the optimum catalytic activity in cyclohexene conversion

SARS-CoV-2 susceptibility and COVID-19 disease severity are associated with genetic variants affecting gene expression in a variety of tissues

Variability in SARS-CoV-2 susceptibility and COVID-19 disease severity between individuals is partly due to genetic factors. Here, we identify 4 genomic loci with suggestive associations for SARS-CoV-2 susceptibility and 19 for COVID-19 disease severity. Four of these 23 loci likely have an ethnicity-specific component. Genome-wide association study (GWAS) signals in 11 loci colocalize with expression quantitative trait loci (eQTLs) associated with the expression of 20 genes in 62 tissues/cell types (range: 1:43 tissues/gene), including lung, brain, heart, muscle, and skin as well as the digestive system and immune system. We perform genetic fine mapping to compute 99% credible SNP sets, which identify 10 GWAS loci that have eight or fewer SNPs in the credible set, including three loci with one single likely causal SNP. Our study suggests that the diverse symptoms and disease severity of COVID-19 observed between individuals is associated with variants across the genome, affecting gene expression levels in a wide variety of tissue types

A first update on mapping the human genetic architecture of COVID-19

peer reviewe

Effect of angiotensin-converting enzyme inhibitor and angiotensin receptor blocker initiation on organ support-free days in patients hospitalized with COVID-19

IMPORTANCE Overactivation of the renin-angiotensin system (RAS) may contribute to poor clinical outcomes in patients with COVID-19. Objective To determine whether angiotensin-converting enzyme (ACE) inhibitor or angiotensin receptor blocker (ARB) initiation improves outcomes in patients hospitalized for COVID-19. DESIGN, SETTING, AND PARTICIPANTS In an ongoing, adaptive platform randomized clinical trial, 721 critically ill and 58 non–critically ill hospitalized adults were randomized to receive an RAS inhibitor or control between March 16, 2021, and February 25, 2022, at 69 sites in 7 countries (final follow-up on June 1, 2022). INTERVENTIONS Patients were randomized to receive open-label initiation of an ACE inhibitor (n = 257), ARB (n = 248), ARB in combination with DMX-200 (a chemokine receptor-2 inhibitor; n = 10), or no RAS inhibitor (control; n = 264) for up to 10 days. MAIN OUTCOMES AND MEASURES The primary outcome was organ support–free days, a composite of hospital survival and days alive without cardiovascular or respiratory organ support through 21 days. The primary analysis was a bayesian cumulative logistic model. Odds ratios (ORs) greater than 1 represent improved outcomes. RESULTS On February 25, 2022, enrollment was discontinued due to safety concerns. Among 679 critically ill patients with available primary outcome data, the median age was 56 years and 239 participants (35.2%) were women. Median (IQR) organ support–free days among critically ill patients was 10 (–1 to 16) in the ACE inhibitor group (n = 231), 8 (–1 to 17) in the ARB group (n = 217), and 12 (0 to 17) in the control group (n = 231) (median adjusted odds ratios of 0.77 [95% bayesian credible interval, 0.58-1.06] for improvement for ACE inhibitor and 0.76 [95% credible interval, 0.56-1.05] for ARB compared with control). The posterior probabilities that ACE inhibitors and ARBs worsened organ support–free days compared with control were 94.9% and 95.4%, respectively. Hospital survival occurred in 166 of 231 critically ill participants (71.9%) in the ACE inhibitor group, 152 of 217 (70.0%) in the ARB group, and 182 of 231 (78.8%) in the control group (posterior probabilities that ACE inhibitor and ARB worsened hospital survival compared with control were 95.3% and 98.1%, respectively). CONCLUSIONS AND RELEVANCE In this trial, among critically ill adults with COVID-19, initiation of an ACE inhibitor or ARB did not improve, and likely worsened, clinical outcomes. TRIAL REGISTRATION ClinicalTrials.gov Identifier: NCT0273570

Oxidation of aliphatic alcohols by using precious metals supported on hydrotalcite under solvent- and base-free conditions

Precious metal nanoparticles supported on magnesium–aluminum hydrotalcite (HT), TiO2, and MgO were prepared by sol immobilization and assessed for the catalytic oxidation of octanol, which is a relatively unreactive aliphatic alcohol, with molecular oxygen as the oxidant under solvent- and base-free conditions. Compared with the TiO2- and MgO-supported catalysts, platinum HT gave the highest activity and selectivity towards the aldehyde. The turnover number achieved for the platinum HT catalyst was >3700 after 180 min under mild reaction conditions. Moreover, the results for the oxidation of different substrates indicate that a specific interaction of octanal with the platinum HT catalyst could lead to deactivation of the catalyst

Gold-based nanoparticulate catalysts for the oxidative esterification of 1,4-butanediol to dimethyl succinate

The effect of the reaction conditions and catalyst composition on the oxidation of 1,4-butanediol has been investigated. We have shown that gold and gold–palladium nanoparticles supported on titania can be effective catalysts for this oxidation reaction. We have demonstrated that the formation of butyrolactone, methyl-4-hydroxybutyrate and dimethyl succinate follow a sequential reaction pathway. We have also investigated the role of acid/base on the reaction and have shown a beneficial synergistic effect of alloying gold with palladium on both the conversion and selectivity towards dimethyl succinate