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The dynamics of the activity and selectivity of bifunctional platinum tungstated zirconia PtWZ catalyst in the hydroisomerization of n-heptane and heptane–benzene mixture is discussed in the paper. The change in the properties of the catalyst before and after reaction were characterized using different techniques. The catalyst showed high efficiency for the hydroisomerization of heptane and heptane–benzene mixture, however, deactivation occurred with time on stream, more significantly when benzene was present in the reaction mixture. The carbonaceous matter was deposited on the catalyst (up to 0.8%) during the hydroisomerization reaction. Predominantly aliphatic carbonaceous «poly-CxHy» species, much less oxidized and little aromatic «graphite-like» species were identified by XPS spectra on the catalyst after the heptane isomerization. In the presence of benzene, the formation of «graphite-like» matter increased progressively as temperature increased. However, no appreciable changes in the bulk properties of the t-ZrO2 matrix (phase composition, specific surface area, pore volume, pore size distribution) and in the state of platinum component were revealed, though an increased extent of W6+ to W5+ reduction was detected by XPS spectra irrespectively of the reaction conditions. The deactivation of the PtWZ catalyst was suggested to result from the blocking the active centers by carbonaceous deposits, the deactivation of the acidic centers being more pronounced as compared to metallic ones. All the carbonaceous deposits were burned-off completely below 450–500 °C.Graphical Abstract

The chemical composition and molecular structure of the pitch-like products obtained by liquid-phase reaction of bituminous coal with heavy hydrocarbon fractions of coal and petroleum origin as solvents at a moderate temperature were comprehensively characterized in terms of a new aromatic feedstock for needle coke and other valuable high-tech carbon materials. The molecular parameters of the products were characterized by using FTIR, 1H NMR, 13C NMR and XPS. Liquid-phase chromatography was used to analyze benzo(a)pyrene (BaP) as a carcinogenicity marker. The chemical composition and the characteristics of the molecular structure of the products were shown to depend greatly on the solvent used. The product obtained using coal tar as a solvent was highly aromatic, its polyaromatic nuclei consisted predominantly of protonated and pericondensed cycles sparsely substituted by CH3 and occasionally CH2 groups. The product obtained using petroleum-derived heavy gas oil as solvent was much less aromatic and prone to autogenous surface oxidation. Its aromatic nuclei contained mainly protonated and highly alkylated catacondensed chains. The intermediate structural parameters were characteristic of the product obtained using binary solvent. A remarkable feature of the pitch-like products obtained was a reduced BaP concentration (up to 40 times compared to typical coal-tar pitch). In terms of the molecular structure, the pitch-like products obtained by low-temperature dissolution of coal can serve as a new polyaromatic feedstock with a reduced carcinogenicity for the production of valuable high-tech carbon materials, needle coke, in particular.

The dynamics of the activity and selectivity of bifunctional platinum tungstated zirconia PtWZ catalyst in the hydroisomerization of n-heptane and heptane–benzene mixture is discussed in the paper. The change in the properties of the catalyst before and after reaction were characterized using different techniques. The catalyst showed high efficiency for the hydroisomerization of heptane and heptane–benzene mixture, however, deactivation occurred with time on stream, more significantly when benzene was present in the reaction mixture. The carbonaceous matter was deposited on the catalyst (up to 0.8%) during the hydroisomerization reaction. Predominantly aliphatic carbonaceous «poly-C x H y » species, much less oxidized and little aromatic «graphite-like» species were identified by XPS spectra on the catalyst after the heptane isomerization. In the presence of benzene, the formation of «graphite-like» matter increased progressively as temperature increased. However, no appreciable changes in the bulk properties of the t -ZrO 2 matrix (phase composition, specific surface area, pore volume, pore size distribution) and in the state of platinum component were revealed, though an increased extent of W 6+ to W 5+ reduction was detected by XPS spectra irrespectively of the reaction conditions. The deactivation of the PtWZ catalyst was suggested to result from the blocking the active centers by carbonaceous deposits, the deactivation of the acidic centers being more pronounced as compared to metallic ones. All the carbonaceous deposits were burned-off completely below 450–500 °C. Graphical Abstract

The dynamics of the activity and selectivity of bifunctional platinum tungstated zirconia PtWZ catalyst in the hydroisomerization of n-heptane and heptane-benzene mixture is discussed in the paper. The change in the properties of the catalyst before and after reaction were characterized using different techniques. The catalyst showed high efficiency for the hydroisomerization of heptane and heptane-benzene mixture, however, deactivation occurred with time on stream, more significantly when benzene was present in the reaction mixture. The carbonaceous matter was deposited on the catalyst (up to 0.8%) during the hydroisomerization reaction. Predominantly aliphatic carbonaceous \"poly-C.sub.xH.sub.y\" species, much less oxidized and little aromatic \"graphite-like\" species were identified by XPS spectra on the catalyst after the heptane isomerization. In the presence of benzene, the formation of \"graphite-like\" matter increased progressively as temperature increased. However, no appreciable changes in the bulk properties of the t-ZrO.sub.2 matrix (phase composition, specific surface area, pore volume, pore size distribution) and in the state of platinum component were revealed, though an increased extent of W.sup.6+ to W.sup.5+ reduction was detected by XPS spectra irrespectively of the reaction conditions. The deactivation of the PtWZ catalyst was suggested to result from the blocking the active centers by carbonaceous deposits, the deactivation of the acidic centers being more pronounced as compared to metallic ones. All the carbonaceous deposits were burned-off completely below 450-500 °C.

The physicochemical properties of the partially spent catalyst Pt-Re-Cl/Al^sub 2^O^sub 3^ reforming of petroleum fractions (R-98 UOP) have been studied. It has been found that during operation of the catalyst, a reduction of textural characteristics, chemical composition, partial phase transformation of alumina support, and accumulation of metallic impurities and carbon deposits take place. The DSC method has been found the presence on the surface of the catalyst of various types of carbonaceous deposits burnable at different temperatures. Their removal is complete at temperatures 500-550 °C.

We describe the construction and characterization of a genomically recoded organism (GRO). We replaced all known UAG stop codons in Escherichia coli MG1655 with synonymous UAA codons, which permitted the deletion of release factor 1 and reassignment of UAG translation function. This GRO exhibited improved properties for incorporation of nonstandard amino acids that expand the chemical diversity of proteins in vivo. The GRO also exhibited increased resistance to T7 bacteriophage, demonstrating that new genetic codes could enable increased viral resistance.

Disruption of the Setx gene, defective in ataxia oculomotor apraxia type 2 (AOA2) leads to the accumulation of DNA/RNA hybrids (R-loops), failure of meiotic recombination and infertility in mice. We report here the presence of R-loops in the testes from other autosomal recessive ataxia mouse models, which correlate with fertility in these disorders. R-loops were coincident in cells showing high basal levels of DNA double strand breaks and in those cells undergoing apoptosis. Depletion of Setx led to high basal levels of R-loops and these were enhanced further by DNA damage both in vitro and in vivo in tissues with proliferating cells. There was no evidence for accumulation of R-loops in the brains of mice where Setx, Atm, Tdp1 or Aptx genes were disrupted. These data provide further evidence for genome destabilization as a consequence of disrupted transcription in the presence of DNA double strand breaks arising during DNA replication or recombination. They also suggest that R-loop accumulation does not contribute to the neurodegenerative phenotype in these autosomal recessive ataxias.

We study the energy-dependent distribution of ultra-high energy cosmic ray arrival directions with respect to luminous matter in the local Universe. We use a specially designed test statistic (TS) that is robust to uncertainties of the galactic magnetic field. We generate realistic mock UHECR sets assuming various injected compositions, and different strengths of the extragalactic magnetic field (EGMF). Applying the TS to both mock sets and the Telescope Array Surface Detector data we constrain, for a given EGMF strength, the UHECR injected mass composition at energies above 10 EeV. At highest energies, higher than 100 EeV, only heavy composition — iron or at least silicon — is compatible with the data, irrespective of the EGMF strength. We then compare the obtained results with the direct Telescope Array fluorescence measurements of the UHECR mass composition. Requiring that the TA composition measurements are compatible with the arrival direction distribution allows us to constrain the parameters of the EGMF. It appears that light composition, measured by TA at around 10 EeV, is compatible with the arrival directions if the EGMF has strength of order 1 nG.

Prior studies have shown that approximately 40% of estrogen receptor positive (ER+) breast cancer (BC) patients harbor immune signaling defects in their blood at diagnosis, and the presence of these defects predicts overall survival. Therefore, it is of interest to quantitatively characterize and measure signaling errors in immune signaling systems in these patients. Here we propose a novel approach combining communication theory and signal processing concepts to model ligand discrimination in immune cells in the peripheral blood. We use the model to measure the specificity of ligand discrimination in the presence of molecular noise by estimating the probability of error, which is the probability of making a wrong ligand identification. We apply our model to the JAK/STAT signaling pathway using high dimensional spectral flow cytometry measurements of transcription factors, including phosphorylated STATs and SMADs, in immune cells stimulated with several cytokines (IFNγ, IL-2, IL-6, IL-4, and IL-10) from 19 ER+ breast cancer patients and 32 healthy controls. In addition, we apply our model to 10 healthy donor samples treated with a clinically approved JAK1/2 inhibitor. Our results show reduced ligand identification accuracy and higher levels of molecular noise in BC patients as compared to healthy controls, which may indicate altered immune signaling and the potential for immune cell dysfunction in these patients. Moreover, the inhibition of JAK1/2 produces a unique pattern of signaling dysfunction, inducing increased ligand detection error rates and reduced signal-to-noise ratios for most immune cell subtypes. These results suggest a means to improve the use of signaling kinase inhibitor therapies by identifying patients with favorable ligand discrimination specificity profiles in their immune cells.

Copper-64 (T1/2 = 12.7 h) is a positron and beta-emitting isotope, with decay characteristics suitable for both positron emission tomography (PET) imaging and radiotherapy of cancer. Copper-67 (T1/2 = 61.8 h) is a beta and gamma emitter, appropriate for radiotherapy β-energy and with a half-life suitable for single-photon emission computed tomography (SPECT) imaging. The chemical identities of 64Cu and 67Cu isotopes allow for convenient use of the same chelating molecules for sequential PET imaging and radiotherapy. A recent breakthrough in 67Cu production opened previously unavailable opportunities for a reliable source of 67Cu with high specific activity and purity. These new opportunities have reignited interest in the use of copper-containing radiopharmaceuticals for the therapy, diagnosis, and theranostics of various diseases. Herein, we summarize recent (2018–2023) advances in the use of copper-based radiopharmaceuticals for PET, SPECT imaging, radiotherapy, and radioimmunotherapy.