C-H Amination Mediated by Cobalt Organoazide Adducts and the Corresponding Cobalt Nitrenoid Intermediates
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We report γ-ray emission from 12 C and 13 C samples irradiated with deuterium-tritium fusion neutrons was experimentally measured at the Omega Laser Facility and at the Ohio University Edwards Accelerator Laboratory. The intent of these measurements was to determine the feasibility of using 13 C-based plastic ablators with embedded 12 C layers for “dark mix” diagnosis of inertial confinement fusion implosions. Spectrally resolved measurements at Ohio University identified significant 4.44-MeV γ-ray emission from the 13 C(n, 2nγ) 12 C-L1 reaction channel. The recorded 4.44-MeV 13 C signal was compared against emission from an identically irradiated 12 C target with known 12 C(n, n'γ) 12 C-L1 cross section, which resulted in an average 13 C(n, 2nγ) 12 C-L1 cross section of 117 ± 17 mb over the incident neutron energy distribution range from 14.4 to 15.8 MeV. Integrated 13C γ -ray signals above 2.9 MeV recorded with the Gas Cherenkov Detector at Omega exceeded MCNP6.1 predictions by a factor of 3. The additional signal was attributed to 4.44-MeV γs resulting in an inferred 13 C(n, 2nγ) 12 C-L1 cross section of 95 ± 11 mb at 14.1-MeV average incident neutron energy. As a result, the 13 C-based “dark mix” diagnostic concept was deemed infeasible.
The potential applications afforded by the generation and reactivity of artificial metalloenzymes (ArMs) in microorganisms are vast. Here we show that a non-pathogenic E. coli strain, Nissle 1917 (EcN), is a suitable host for the creation of ArMs from cytochrome P450s and artificial heme cofactors. An outer-membrane receptor in EcN transports an iridium porphyrin into the cell, and the Ir-CYP119 (CYP119 containing iridium porphyrin) assembled in vivo catalyzes carbene insertions into benzylic C-H bonds enantioselectively and site-selectively. The application of EcN as a whole-cell screening platform eliminates the need for laborious processing procedures, drastically increases the ease and throughput of screening, and accelerates the development of Ir-CYP119 with improved catalytic properties. Studies to identify the transport machinery suggest that a transporter different from the previously assumed ChuA receptor serves to usher the iridium porphyrin into the cytoplasm.
For E. coli, C. thermocellum, Z. mobilis: shotgun proteomics analyses of tryptic digests of cell lysates; direct infusion of cell lysates spiked with isotopically labelled peptides to perform absolute quantification of specific proteins of interest, primarily related to glycolysis
Using a data sample corresponding to an integrated luminosity of 10.9 fb − 1 collected at center-of-mass energies from 4.16 to 4.34 GeV with the BESIII detector, we search for the decay χ c 1 ( 3872 ) → π + π − χ c 1 in the radiative production e + e − → γ χ c 1 ( 3872 ) . No significant signal is observed, and the ratio for the branching fraction of χ c 1 ( 3872 ) → π + π − χ c 1 to χ c 1 ( 3872 ) → π + π − J / ψ is measured as R ≡ B [ χ c 1 ( 3872 ) → π + π − χ c 1 ] B [ χ c 1 ( 3872 ) → π + π − J / ψ ] < 0.18 at 90% confidence level. An upper limit on the product of the cross section σ [ e + e − → γ χ c 1 ( 3872 ) ] and the branching fraction B [ χ c 1 ( 3872 ) → π + π − χ c 1 ] at each center-of-mass energy is also given. These measurements favor the nonconventional charmonium nature of the χ c 1 ( 3872 ) state. Published by the American Physical Society 2024
We present a study of a singly Cabibbo-suppressed decay Λ$^+_c$ → pK$^0_S$K$^0_S$ and a Cabibbo-favored decay Λ$^+_c$ → pK$^0_S$η based on 980 fb -1 of data collected by the Belle detector, operating at the KEKB energy-asymmetric e + e - collider. We measure their branching fractions relative to Λ$^+_c$ → pK$^0_S$: $\mathscr{B}$(Λ$^+_c$ → pK$^0_S$K$^0_S$)/$\mathscr{B}$(Λ$^+_c$ → pK$^0_S$) = (1.48 ± 0.08 ± 0.04) × 10 -2 and $\mathscr{B}$(Λ$^+_c$ → pK$^0_S$η)/$\mathscr{B}$(Λ$^+_c$ → pK$^0_S$) = (2.73 ± 0.06 ± 0.13) × 10 -1 . Combining with the world average $\mathscr{B}$(Λ$^+_c$ → pK$^0_S$), we have the absolute branching fractions, $\mathscr{B}$(Λ$^+_c$ → pK$^0_S$K$^0_S$) = (2.35 ± 0.12 ± 0.07 ± 0.12) × 10 -4 and $\mathscr{B}$(Λ$^+_c$ → pK$^0_S$η) = (4.35 ± 0.10 ± 0.20 ± 0.22) × 10 -3 . The first and second uncertainties are statistical and systematic, respectively, while the third ones arise from the uncertainty on $\mathscr{B}$(Λ$^+_c$ → pK$^0_S$). The mode Λ$^+_c$ → pK$^0_S$K$^0_S$ is observed for the first time and has a statistical significance of >10σ. The branching fraction of Λ$^+_c$ → pK$^0_S$η has been measured with a threefold improvement in precision over previous results and is found to be consistent with the world average.
We present the first search for the weak radiative decays Λ$^+_c$ → Σ + γ and Ξ$^0_c$ → Ξ 0 γ using a data sample of 980 fb -1 collected by the Belle detector operating at the KEKB asymmetric-energy e + e - collider. There are no evident Λ$^+_c$ → Σ + γ or Ξ$^0_c$ → Ξ 0 γ signals. Taking the decays Λ$^+_c$ → pK - π + and Ξ$^0_c$ → Ξ - π + as normalization channels, the upper limits at 90% credibility level on the ratios of branching fractions $\mathcal{B}$(Λ$^+_c$ → Σ + γ)/$\mathcal{B}$(Λ$^+_c$ → pK - π + ) < 4.0 x 10 -3 and $\mathcal{B}$(Ξ$^0_c$ → Ξ 0 γ)/$\mathcal{B}$(Ξ$^0_c$ → Ξ - π + ) < 1.2 x 10 -2 are determined. We obtain the upper limits at 90% credibility level on the absolute branching fractions $\mathcal{B}$(Λ$^+_c$ → Σ + γ) < 2.6 x 10 -4 and $\mathcal{B}$(Ξ$^0_c$ → Ξ 0 γ) < 1.8 x 10 -4 .
The purification of C 2 H 4 from C 2 H 6 /C 2 H 4 /C 2 H 2 mixtures is of great significance in the chemical industry for C 2 H 4 production but remains a daunting task. Guided by powerful reticular chemistry principles, herein a systematic study is carried out to engineer pore dimensions and pore functionality of fcu-type Y-based metal–organic frameworks (Y-MOFs) through the construction of a series of eight new structures using linear dicarboxylate linkers with different length and functional groups. This study illustrates how delicate changes in pore size and pore surface chemistry can effectively influence the adsorption preference of C 2 H 6 , C 2 H 4 , and C 2 H 2 by the MOFs. Importantly, clear relations between pore size/pore surface polarity and C 2 adsorption selectivities of this series of MOFs are established. In particular, HIAM-326 built on a linker decorated with trifluoromethoxy group shows notably preferential adsorption of C 2 H 6 and C 2 H 2 over C 2 H 4 , with balanced C 2 H 2 /C 2 H 4 and C 2 H 6 /C 2 H 4 selectivities. Furthermore, this endows the compound with the capability of one-step purification of C 2 H 4 from C 2 H 6 /C 2 H 4 /C 2 H 2 ternary mixtures, which is validated by breakthrough measurements where high purity C 2 H 4 (99.9%+) can be obtained directly from the separation column. Its adsorption thermodynamics and underlying selective adsorption mechanisms are further revealed by ab initio calculations.
The photodissociation dynamics of astrophysically relevant propyl derivatives (C 3 H 7 X; X = CN, OH, HCO) at 157 nm exploiting an ultracompact velocity map imaging (UVMIS) setup has been reported. The successful operation of UVMIS allowed the exploration of the 157 nm photo dissociation of six (iso)propyl systems - n/i-propyl cyanide (C 3 H 7 CN), n/i-propyl alcohol (C 3 H 7 OH), and (iso)butanal (C 3 H 7 CHO) – to explore the C 3 H 7 loss channel. The distinct center-of-mass translational energy distributions for the i-C 3 H 7 X (X= CN, OH, HCO) could be explained through preferential excitation of the low frequency C-H bending modes of the formyl moiety compared to the higher frequency stretchings of the cyano and hydroxy moieties. Although the ionization energy of the n-C 3 H 7 radical exceeds the energy of a 157 nm photon, C 3 H 7 + was observed in the n-C 3 H 7 X (X= CN, OH, HCO) systems as a result of photoionization of vibrationally "hot" n-C 3 H 7 fragments, photoionization of i-C 3 H 7 after a hydrogen shift in vibrationally "hot" n-C 3 H 7 radicals, and/or two-photon ionization. Our experiments reveal that at least the isopropyl radical (i-C 3 H 7 ) and possibly the normal propyl radical (n-C 3 H 7 ) should be present in the interstellar medium and hence searched for by radio telescopes.
Synthesis of the first thorium-containing clusterfullerenes, ThC 2 @C s (6)–C 82 and ThC 2 @C 2 (5)–C 82 , is reported. These two novel actinide fullerene compounds were characterized by mass spectrometry, single-crystal X-ray diffraction crystallography, UV–vis–NIR spectroscopy, and theoretical calculations. Crystallographic studies reveal that the encapsulated ThC 2 clusters in both C s (6)–C 82 and C 2 (5)–C 82 feature a novel bonding structure with one thorium metal center connected by a C≡C unit, forming an isosceles triangular configuration, which has not been hitherto observed for endohedral fullerenes or for solid phase thorium carbides. Electronic structure calculations assign a formal electronic structure of [Th 4+ (C 2 ) 2- ] 2+ @[C 82 ] 2- , with pronounced donation bonding from (C 2 ) 2- to Th 4+ , secondary backbonding from the fullerene to thorium and Th–C double bond character in both compounds. This work presents a new family of endohedral fullerenes, MC 2 @C 2n-2 , being unexpected isomers of MC 2n , and provides broader understanding of thorium bonding.
The N 4 -methylation of cytidine (m 4 C and m 4 2 C) in RNA plays important roles in both bacterial and eukaryotic cells. In this work, we synthesized a series of m 4 C and m 4 2 C modified RNA oligonucleotides, conducted their base pairing and bioactivity studies, and solved three new crystal structures of the RNA duplexes containing these two modifications. Our thermostability and X-ray crystallography studies, together with the molecular dynamic simulation studies, demonstrated that m 4 C retains a regular C:G base pairing pattern in RNA duplex and has a relatively small effect on its base pairing stability and specificity. By contrast, the m 4 2 C modification disrupts the C:G pair and significantly decreases the duplex stability through a conformational shift of native Watson-Crick pair to a wobble-like pattern with the formation of two hydrogen bonds. This double-methylated m 4 2 C also results in the loss of base pairing discrimination between C:G and other mismatched pairs like C:A, C:T and C:C. The biochemical investigation of these two modified residues in the reverse transcription model shows that both mono- or di-methylated cytosine bases could specify the C:T pair and induce the G to T mutation using HIV-1 RT. In the presence of other reverse transcriptases with higher fidelity like AMV-RT, the methylation could either retain the normal nucleotide incorporation or completely inhibit the DNA synthesis. These results indicate the methylation at N 4 -position of cytidine is a molecular mechanism to fine tune base pairing specificity and affect the coding efficiency and fidelity during gene replication.
Development of platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) has been a strategic research topic for proton exchange membrane (PEM) fuel cells. Present state-of-art PGM-free ORR catalysts are Fe, N co-doped carbon (Fe-N-C) catalysts, which unfortunately exhibit instability concerns. Herein, we report a stable atomically dispersed Co, N co-doped carbon (Co-N-C) catalyst with high Co content of 1.0 at% and the active site, i.e., the coordination of Co, is CoN2+2 in nature. The Co-N-C catalyst demonstrated high ORR activity comparable to, and high stability over 3 times better than, that of the Fe-N-C catalyst. It also achieved a high activity of 22 mA cm2 at 0.9 ViR-free and a power density of 0.61 W cm-2 under 1.0 bar H2/O2. Further, we identify two main degradation mechanisms of the PGM-free catalysts: catalyst oxidation by H2O2/radicals and demetalation. The improved stability of Co-N-C relative to Fe-N-C is attributed to less Fenton-reactive nature of Co and significantly enhanced resistance to demetalation of Co-N-C.
We report the results of the first search for B − decays to the Ξ ¯ c 0 Λ ¯ c − final state using 711 fb − 1 of data collected at the ϒ ( 4 S ) resonance with the Belle detector at the KEKB asymmetric-energy e + e − collider. The results are interpreted in terms of both direct baryon-number-violating B − decay and Ξ c 0 − Ξ ¯ c 0 oscillations which follow the standard model decay B − → Ξ c 0 Λ ¯ c − . We observe no evidence for baryon number violation and set the 95% confidence-level upper limits on the ratio of baryon-number-violating and standard model branching fractions B ( B − → Ξ ¯ c 0 Λ ¯ c − ) / B ( B − → Ξ c 0 Λ ¯ c − ) to be < 2.7 % and on the effective angular frequency of mixing ω in Ξ c 0 − Ξ ¯ c 0 oscillations to be < 0.76 ps − 1 (equivalent to τ mix > 1.3 ps ). Published by the American Physical Society 2024
A study of ${B}_c^{+}\to J/\psi {D}_s^{+}$ and ${B}_c^{+}\to J/\psi {D}_s^{\ast +}$ decays using 139 fb –1 of integrated luminosity collected with the ATLAS detector from $\sqrt{s}$ = 13 TeV pp collisions at the LHC is presented. The ratios of the branching fractions of the two decays to the branching fraction of the ${B}_c^{+}$ → J/ψπ + decay are measured: $\mathcal{B}\left({B}_c^{+}\to J/\psi {D}_s^{+}\right)/\mathcal{B}\left({B}_c^{+}\to J/{\psi \pi}^{+}\right)$ = 2.76 ± 0.47 and $\mathcal{B}\left({B}_c^{+}\to J/\psi {D}_s^{\ast +}\right)/\mathcal{B}\left({B}_c^{+}\to J/{\psi \pi}^{+}\right)$ = 5.33 ± 0.96. The ratio of the branching fractions of the two decays is found to be $\mathcal{B}\left({B}_c^{+}\to J/\psi {D}_s^{\ast +}\right)/\mathcal{B}\left({B}_c^{+}\to J/\psi {D}_s^{\ast +}\right)$ = 1.93 ± 0.26. For the ${B}_c^{+}\to J/\psi {D}_s^{\ast +}$ decay, the transverse polarization fraction, Γ ±± /Γ, is measured to be 0.70 ± 0.11. The reported uncertainties include both the statistical and systematic components added in quadrature. The precision of the measurements exceeds that in all previous studies of these decays. These results supersede those obtained in the earlier ATLAS study of the same decays with $\sqrt{s}$ = 7 and 8 TeV pp collision data. A comparison with available theoretical predictions for the measured quantities is presented.
The total charm-quark production cross section per unit of rapidity dσ($\mathbf {c\overline{c}}$)/dy, and the fragmentation fractions of charm quarks to different charm-hadron species f(c → h c ), are measured for the first time in p–Pb collisions at $\sqrt{s_{NN}}$ = 5.02 TeV at midrapidity (–0.96 < y < 0.04 in the centre-of-mass frame) using data collected by ALICE at the CERN LHC. The results are obtained based on all the available measurements of prompt production of ground-state charm-hadron species: D 0 , D + , D$^{+}_{s}$, and J/ψ mesons, and Λ$^{+}_{c}$ and $Ξ$$^{0}_{c}$ baryons. The resulting cross section is dσ($\mathbf {c\overline{c}}$)/dy = 219.6 ± 6.3 (stat.) $^{+10.5}_{–11.8}$ (syst.) $^{+8.3}_{–2.9}$ (extr.) ± 5.4 (BR) ± 4.6 (lumi.) ± 19.5 (rapidity shape) + 15.0 (Ω$^{0}_{c}$) mb, which is consistent with a binary scaling of pQCD calculations from pp collisions. The measured fragmentation fractions are compatible with those measured in pp collisions at $\sqrt{s_{NN}}$ = 5.02 and 13 TeV, showing an increase in the relative production rates of charm baryons with respect to charm mesons in pp and p–Pb collisions compared with e + e – and e – p collisions. The p T -integrated nuclear modification factor of charm quarks, R pPb ($\mathbf {c\overline{c}}$) = 0.91 ± 0.04 (stat.) $^{+0.08}_{–0.09}$ (syst.) $^{+0.05}_{–0.03}$ (extr.) ± 0.03 (lumi.), is found to be consistent with unity and with theoretical predictions including nuclear modifications of the parton distribution functions.
Distinguishing biotic compounds from abiotic ones is important in resource geology, biogeochemistry, and the search for life in the universe. Stable isotopes have traditionally been used to discriminate the origins of organic materials, with particular focus on hydrocarbons. However, despite extensive efforts, unequivocal distinction of abiotic hydrocarbons remains challenging. Recent development of clumped-isotope analysis provides more robust information because it is independent of the stable isotopic composition of the starting material. Here, we report data from a 13 C- 13 C clumped-isotope analysis of ethane and demonstrate that the abiotically-synthesized ethane shows distinctively low 13 C- 13 C abundances compared to thermogenic ethane. A collision frequency model predicts the observed low 13 C- 13 C abundances (anti-clumping) in ethane produced from methyl radical recombination. In contrast, thermogenic ethane presumably exhibits near stochastic 13 C- 13 C distribution inherited from the biological precursor, which undergoes C-C bond cleavage/recombination during metabolism. Further, we find an exceptionally high 13 C- 13 C signature in ethane remaining after microbial oxidation. In summary, the approach distinguishes between thermogenic, microbially altered, and abiotic hydrocarbons. The 13 C- 13 C signature can provide an important step forward for discrimination of the origin of organic molecules on Earth and in extra-terrestrial environments.
The mitochondrial electron transport chain (ETC) of Plasmodium malaria parasites is a major antimalarial drug target, but critical cytochrome (cyt) functions remain unstudied and enigmatic. Parasites express two distinct cyt c homologs (c and c-2) with unusually sparse sequence identity and uncertain fitness contributions. P. falciparum cyt c-2 is the most divergent eukaryotic cyt c homolog currently known and has sequence features predicted to be incompatible with canonical ETC function. We tagged both cyt c homologs and the related cyt c1 for inducible knockdown. Translational repression of cyt c and cyt c1 was lethal to parasites, which died from ETC dysfunction and impaired ubiquinone recycling. In contrast, cyt c-2 knockdown or knockout had little impact on blood-stage growth, indicating that parasites rely fully on the more conserved cyt c for ETC function. Biochemical and structural studies revealed that both cyt c and c-2 are hemylated by holocytochrome c synthase, but UV-vis absorbance and EPR spectra strongly suggest that cyt c-2 has an unusually open active site in which heme is stably coordinated by only a single axial amino acid ligand and can bind exogenous small molecules. These studies provide a direct dissection of cytochrome functions in the ETC of malaria parasites and identify a highly divergent Plasmodium cytochrome c with molecular adaptations that defy a conserved role in eukaryotic evolution.
Here, we report a study of Λ$^+_c$ → Λ h + and Λ$^+_c$ → Σ 0 h + ( h = K, π ) decays based on a data sample of 980 fb -1 collected with the Belle detector at the KEKB energy-asymmetric e + e - collider. The first results of direct CP asymmetry in two-body singly Cabibbo-suppressed (SCS) decays of charmed baryons are measured, A$^{dir}_{CP}(Λ^+_{c} → ΛK^{+})$ = +0.021 ± 0.026 ± 0.001 and A$^{dir}_{CP}(Λ^+_{c} → Σ^{0}K^{+})$ = +0.025 ± 0.054 ± 0.004. We also make the most precise measurement of the decay asymmetry parameters (α) for the four modes of interest and search for CP violation via the α-induced CP asymmetry (A$^α_{CP}$ ). We measure A$^α_{CP}$ ($Λ^+_{c} → ΛK^{+}$) = -0.023 ± 0.086 ± 0.071 and A$^α_{CP}$ ($Λ^+_{c} → Σ^{0}K^{+}$) = +0.08 ± 0.35 ± 0.14, which are the first A$^α_{CP}$ results for SCS decays of charmed baryons. We search for Λ -hyperon CP violation in $Λ^+_{c}$ → (Λ, Σ 0 )π + and find A$^α_{CP}$(Λ → pπ - ) = +0.013 ± 0.007 ± 0.011 . This is the first time that hyperon CP violation has been measured via Cabibbo-favored charm decays. No evidence of baryon CP violation is found. We also obtain the most precise branching fractions for two SCS Λ$^+_c$ decays, $\mathscr{B}$($Λ^+_{c} → ΛK^{+}$) = (6.57 ± 0.17 ± 0.11 ± 0.35) x 10 -4 and $\mathscr{B}$($Λ^+_{c} → Σ^{0}K^{+}$) = (3.58 ± 0.19 ±0.06 ±0.19) x 10 -4 . The first uncertainties are statistical and the second systematic, while the third uncertainties come from the uncertainties on the world average branching fractions of $Λ^+_{c}$ → (Λ, Σ 0 )π + .