The effect of support in Ir-ReO
x
catalysts
for glycerol hydrogenolysis to 1,3-propanediol was investigated. Rutile
TiO2 support showed high activity, even higher than previously
reported SiO2 support. Anatase TiO2, C, ZrO2, CeO2, Al2O3, and MgO supports
showed very low activity of supported Ir-ReO
x
pairs. Higher Ir-based 1,3-propanediol productivity of Ir-ReO
x
/rutile catalyst was obtained at the initial
stage even with lower Re/Ir ratio (typical Ir loading amount, 4 wt
%, nominal ratio of 0.25; actual ratio of 0.24) without addition of
H2SO4 than that of Ir-ReO
x
/SiO2. The 1,3-propanediol productivity over Ir-ReO
x
catalysts showed dependency on catalyst
compositions (metal loading amount), and the relationship between
catalyst structure and activity was further established over Ir-ReO
x
/rutile. Relatively high Ir loading amount
in comparison with small surface area (6 wt %, on 6 m2 g–1 rutile TiO2) showed the highest activity
(Ir-based activity). From combined characterization results altogether
(TPR, TEM, XPS, XAS, CO adsorption, CO FT-IR) with a kinetics study,
the Ir metal particles interacted with the partially oxidized ReO
x
cluster (average valence of Re: +3) almost
totally covering the surface of rutile TiO2 particles,
and the active site was the Ir-ReO
x
interface.
Small amounts of Ir species (∼20%) were incompletely reduced;
however, such IrO
x
species as well as
rutile TiO2 support were not directly involved in glycerol
hydrogenolysis. The role of rutile support was regarded as providing
a unique environment for stabilization of uniform and small Ir-ReO
x
particles with very high surface density
on rutile TiO2, which increased the number of active sites
per Re amount.
Background: This study was aimed at evaluating the clinical significance of serum HBV RNA, hepatitis B corerelated antigen (HBcrAg) and hepatitis B core antibody (anti-HBc) levels in chronic hepatitis B patients with undetectable HBV DNA during nucleoside/nucleotide analogue (NA) treatment. Methods: Fifty-seven patients who received long-term NA treatment of median 5.83 (25%, 75% percentiles 4.67, 7.75) years were enrolled, and 285 serum samples at five time points for each patient were quantitatively analysed for the three serum markers together with serum HBV DNA and hepatitis B surface antigen (HBsAg) levels. Results: The HBV RNA level significantly correlated with HBcrAg (r=0.629; P<0.001) but not HBsAg levels (P=0.1460). Nonetheless, the HBcrAg level significantly correlated with the HBsAg level (r=0.469; P<0.001). Hepatitis B e antigen (HBeAg)-positive samples showed higher HBV RNA, HBcrAg and HBsAg levels than HBeAgnegative samples did (all P<0.05). Nine patients with HBeAg loss manifested a significantly greater decline in HBV RNA and HBcrAg levels (median 1.84 [25%, 75% percentiles 1.02, 2.12] log 10 copies/ml, 1.14 [0.62, 2.21] log 10 U/ml, respectively) compared with those in seven patients without HBeAg loss (0.74 [0.10, 1.08] log 10 copies/ml and 0.41 [0.21, 0.69] log 10 U/ml, respectively). Overall, serum HBV RNA, HBcrAg, HBsAg and anti-HBc levels gradually decreased with time during NA treatment. At the end of observation, HBV RNA and HBcrAg reached an undetectable level in 26 and 6 (46% and 11%) patients, respectively. Conclusions: Monitoring of HBV RNA and HBcrAg levels is useful for NA-treated patients with undetectable HBV DNA. The attainment of HBV RNA undetectability usually occurs prior to HBcrAg undetectability.
Herein, we report that genetically programmable fusion cellular vesicles (Fus‐CVs) displaying high‐affinity SIRPα variants and PD‐1 can activate potent antitumor immunity through both innate and adaptive immune effectors. Dual‐blockade of CD47 and PD‐L1 with Fus‐CVs significantly increases the phagocytosis of cancer cells by macrophages, promotes antigen presentation, and activates antitumor T‐cell immunity. Moreover, the bispecific targeting design of Fus‐CVs ensures better targeting on tumor cells, but less on other cells, which reduces systemic side effects and enhances therapeutic efficacies. In malignant melanoma and mammary carcinoma models, we demonstrate that Fus‐CVs significantly improve overall survival of model animals by inhibiting post‐surgery tumor recurrence and metastasis. The Fus‐CVs are suitable for protein display by genetic engineering. These advantages, integrated with other unique properties inherited from source cells, make Fus‐CVs an attractive platform for multi‐targeting immune checkpoint blockade therapy.
In many reactions restricted by water, selective removal of water from the reaction system is critical and usually requires a membrane reactor. We found that a simple physical mixture of hydrophobic poly(divinylbenzene) with cobalt-manganese carbide could modulate a local environment of catalysts for rapidly shipping water product in syngas conversion. We were able to shift the water-sorption equilibrium on the catalyst surface, leading to a greater proportion of free surface that in turn raised the rate of syngas conversion by nearly a factor of 2. The carbon monoxide conversion reached 63.5%, and 71.4% of the hydrocarbon products were light olefins at 250°C, outperforming poly(divinylbenzene)-free catalyst under equivalent reaction conditions. The physically mixed CoMn carbide/poly(divinylbenzene) catalyst was durable in the continuous test for 120 hours.
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