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At least 1,333 records · Page 74
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

c-Fos is necessary for HGF-mediated gene regulation and cell migration in Schwann cells

Highlights: • HGF up-regulates c-Fos expression in distal SCs in injured sciatic nerves. • HGF increase c-Fos expression in primary Schwann cells. • HGF induce c-Fos expression in SCs by ERK/CREB pathway. • c-Fos protein has role in various HGF-mediated responses in SCs. We previously reported that the expression of hepatocyte growth factor (HGF) was highly induced after peripheral nerve damage, and that c-Fos is one of many cellular genes whose expressions are affected by the increased level of HGF[1]. c-Fos is an important component of AP-1 heterodimer, but its role has not been clearly understood in the context of HGF and Schwann cells (SCs). In this study, we investigated the relationship between HGF and c-Fos. First, it was confirmed that the c-Fos was increased in SCs after nerve injury, while this effect abrogated by PHA-665752, an inhibitor of c-met receptor. When primary SCs were treated with recombinant HGF protein, c-Fos expression was regulated in a typical quick, transient fashion at both RNA and proteins levels. HGF-mediated induction of c-Fos expression was highly suppressed by specific inhibitors of ERK and CREB, respectively. The knock down of c-Fos expression by siRNA almost completely blocked various HGF-mediated effects in SCs, such as induction of gene expression of GDNF, LIF, and c-Myc, and migration of SCs, indicating that c-Fos might play a key role in HGF effects. Taken together, our results suggested that c-Fos plays a key role(s) in HGF-mediated effects on neurotrophic genes and cell migration.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

c-Met Expression Is a Marker of Poor Prognosis in Patients With Locally Advanced Head and Neck Squamous Cell Carcinoma Treated With Chemoradiation

Purpose: To examine the prognostic significance of c-Met expression in relation to p16 and epidermal growth factor receptor (EGFR) in patients with locally advanced head and neck squamous cell carcinoma (HNSCC) treated with definitive concurrent chemoradiation. Methods and Materials: Archival tissue from 107 HNSCC patients treated with chemoradiation was retrieved, and a tissue microarray was assembled. Immunohistochemical staining of c-Met, p16, and EGFR was performed. c-Met expression was correlated with p16, EGFR, clinical characteristics, and clinical endpoints including locoregional control (LRC), distant metastasis (DM), disease-free survival (DFS), and overall survival (OS). Results: Fifty-one percent of patients were positive for p16, and 53% were positive for EGFR. Both p16-negative (P≤.001) and EGFR-positive (P=.019) status predicted for worse DFS. Ninety-three percent of patients stained positive for c-Met. Patients were divided into low (0, 1, or 2+ intensity) or high (3+ intensity) c-Met expression. On univariate analysis, high c-Met expression predicted for worse LRC (hazard ratio [HR] 2.27; 95% CI, 1.08-4.77; P=.031), DM (HR 4.41; 95% CI, 1.56-12.45; P=.005), DFS (HR 3.00; 95% CI, 1.68-5.38; P<.001), and OS (HR 4.35; 95% CI, 2.13-8.88; P<.001). On multivariate analysis, after adjustment for site, T stage, smoking history, and EGFR status, only high c-Met expression (P=.011) and negative p16 status (P=.003) predicted for worse DFS. High c-Met expression was predictive of worse DFS in both EGFR-positive (P=.032) and -negative (P=.008) patients. In the p16-negative patients, those with high c-Met expression had worse DFS (P=.036) than did those with low c-Met expression. c-Met expression was not associated with any outcome in the p16-positive patients. Conclusions: c-Met is expressed in the majority of locally advanced HNSCC cases, and high c-Met expression predicts for worse clinical outcomes. High c-Met expression predicted for worse DFS in p16-negative patients but not in p16-positive patients. c-Met predicted for worse outcome regardless of EGFR status.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2017

Neutral carbon emission in luminous infrared galaxies: the [C i] lines as total molecular gas tracers

We present a statistical study of the [C i] ({sup 3}P{sub 1} → {sup 3}P{sub 0}), [C i] ({sup 3}P{sub 2} → {sup 3}P{sub 1}) lines (hereafter [C i] (1–0) and [C i] (2–1), respectively) and the CO(1–0) line for a sample of (ultra-)luminous infrared galaxies ((U)LIRGs). We explore the correlations between the luminosities of CO(1–0) and [C i] lines, and find that L{sub CO(1−0)}{sup ′} correlates almost linearly with both L{sub [C I](1−0)}{sup ′} and L{sub [C I](2−1)}{sup ′}, suggesting that [C i] lines can trace total molecular gas mass, at least for (U)LIRGs. We also investigate the dependence of L{sub [C I](1−0)}{sup ′}/L{sub CO(1−0)}{sup ′}, L{sub [C I](2−1)}{sup ′}/L{sub CO(1−0)}{sup ′}, and L{sub [C I](2−1)}{sup ′}/L{sub [C I](1−0)}{sup ′} on the far-infrared color of 60-to-100 μm, and find non-correlation, a weak correlation, and a modest correlation, respectively. Under the assumption that these two carbon transitions are optically thin, we further calculate the [C i] line excitation temperatures, atomic carbon masses, and mean [C i] line flux-to-H{sub 2} mass conversion factors for our sample. The resulting H{sub 2} masses using these [C i]-based conversion factors roughly agree with those derived from L{sub CO(1−0)}{sup ′} and CO-to-H{sub 2} conversion factor.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Large fluxes and rapid turnover of mineral-associated carbon across topographic gradients in a humid tropical forest: insights from paired 14 C analysis

It has been proposed that the large soil carbon (C) stocks of humid tropical forests result predominantly from C stabilization by reactive minerals, whereas oxygen (O 2 ) limitation of decomposition has received much less attention. We examined the importance of these factors in explaining patterns of C stocks and turnover in the Luquillo Experimental Forest, Puerto Rico, using radiocarbon ( 14 C) measurements of contemporary and archived samples. Samples from ridge, slope, and valley positions spanned three soil orders (Ultisol, Oxisol, Inceptisol) representative of humid tropical forests, and differed in texture, reactive metal content, O 2 availability, and root biomass. Mineral-associated C comprised the large majority (87 ± 2%, n = 30) of total soil C. Turnover of most mineral-associated C (66 ± 2%) was rapid (11 to 26 years; mean and SE: 18 ± 3 years) in 25 of 30 soil samples across surface horizons (0–10 and 10–20 cm depths) and all topographic positions, independent of variation in reactive metal concentrations and clay content. Passive C with centennial–millennial turnover was typically much less abundant (34 ± 3%), even at 10–20 cm depths. Carbon turnover times and concentrations significantly increased with concentrations of reduced iron (Fe(II)) across all samples, suggesting that O 2 availability may have limited the decomposition of mineral-associated C over decadal scales. Steady-state inputs of mineral-associated C were statistically similar among the three topographic positions, and could represent 10–25% of annual litter production. Observed trends in mineral-associated Δ 14 C over time could not be fit using the single-pool model used in many other studies, which generated contradictory relationships between turnover and Δ 14 C as compared with a more realistic two-pool model. The large C fluxes in surface and near-surface soils documented here are supported by findings from paired 14 C studies in other types of ecosystems, and suggest that most mineral-associated C cycles relatively rapidly (decadal scales) across ecosystems that span a broad range of state factors.

Hall, S. J.↗
DOE OSTI2015

Acetylation of the c-MYC oncoprotein is required for cooperation with the HTLV-1 p30{sup II} accessory protein and the induction of oncogenic cellular transformation by p30{sup II}/c-MYC

The human T-cell leukemia retrovirus type-1 (HTLV-1) p30{sup II} protein is a multifunctional latency-maintenance factor that negatively regulates viral gene expression and deregulates host signaling pathways involved in aberrant T-cell growth and proliferation. We have previously demonstrated that p30{sup II} interacts with the c-MYC oncoprotein and enhances c-MYC-dependent transcriptional and oncogenic functions. However, the molecular and biochemical events that mediate the cooperation between p30{sup II} and c-MYC remain to be completely understood. Herein we demonstrate that p30{sup II} induces lysine-acetylation of the c-MYC oncoprotein. Acetylation-defective c-MYC Lys→Arg substitution mutants are impaired for oncogenic transformation with p30{sup II} in c-myc{sup −/−} HO15.19 fibroblasts. Using dual-chromatin-immunoprecipitations (dual-ChIPs), we further demonstrate that p30{sup II} is present in c-MYC-containing nucleoprotein complexes in HTLV-1-transformed HuT-102 T-lymphocytes. Moreover, p30{sup II} inhibits apoptosis in proliferating cells expressing c-MYC under conditions of genotoxic stress. These findings suggest that c-MYC-acetylation is required for the cooperation between p30{sup II}/c-MYC which could promote proviral replication and contribute to HTLV-1-induced carcinogenesis. - Highlights: • Acetylation of c-MYC is required for oncogenic transformation by HTLV-1 p30{sup II}/c-MYC. • Acetylation-defective c-MYC mutants are impaired for foci-formation by p30{sup II}/c-MYC. • The HTLV-1 p30{sup II} protein induces lysine-acetylation of c-MYC. • p30{sup II} is present in c-MYC nucleoprotein complexes in HTLV-1-transformed T-cells. • HTLV-1 p30{sup II} inhibits apoptosis in c-MYC-expressing proliferating cells.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Carbon dynamics of mature and regrowth tropical forests derived from a pantropical database ( T rop F or C ‐db)

Abstract Tropical forests play a critical role in the global carbon (C) cycle, storing ~45% of terrestrial C and constituting the largest component of the terrestrial C sink. Despite their central importance to the global C cycle, their ecosystem‐level C cycles are not as well‐characterized as those of extra‐tropical forests, and knowledge gaps hamper efforts to quantify C budgets across the tropics and to model tropical forest‐climate interactions. To advance understanding of C dynamics of pantropical forests, we compiled a new database, the Tropical Forest C database (TropForC‐db), which contains data on ground‐based measurements of ecosystem‐level C stocks and annual fluxes along with disturbance history. This database currently contains 3568 records from 845 plots in 178 geographically distinct areas, making it the largest and most comprehensive database of its type. Using TropForC‐db, we characterized C stocks and fluxes for young, intermediate‐aged, and mature forests. Relative to existing C budgets of extra‐tropical forests, mature tropical broadleaf evergreen forests had substantially higher gross primary productivity ( GPP ) and ecosystem respiration (R eco ), their autotropic respiration (R a ) consumed a larger proportion (~67%) of GPP , and their woody stem growth ( ANPP stem ) represented a smaller proportion of net primary productivity ( NPP , ~32%) or GPP (~9%). In regrowth stands, aboveground biomass increased rapidly during the first 20 years following stand‐clearing disturbance, with slower accumulation following agriculture and in deciduous forests, and continued to accumulate at a slower pace in forests aged 20–100 years. Most other C stocks likewise increased with stand age, while potential to describe age trends in C fluxes was generally data‐limited. We expect that TropForC‐db will prove useful for model evaluation and for quantifying the contribution of forests to the global C cycle. The database version associated with this publication is archived in Dryad ( DOI : 10.5061/dryad.t516f ) and a dynamic version is maintained at https://github.com/forc-db .

Anderson‐Teixeira, Kristina J.↗
DOE OSTI2016

The draft genome of the C 3 panicoid grass species Dichanthelium oligosanthes

Comparisons between C 3 and C 4 grasses often utilize C 3 species from the subfamilies Ehrhartoideae or Pooideae and C 4 species from the subfamily Panicoideae, two clades that diverged over 50 million years ago. The divergence of the C 3 panicoid grass Dichanthelium oligosanthes from the independent C 4 lineages represented by Setaria viridis and Sorghum bicolor occurred approximately 15 million years ago, which is significantly more recent than members of the Bambusoideae, Ehrhartoideae, and Pooideae subfamilies. D. oligosanthes is ideally placed within the panicoid clade for comparative studies of C 3 and C 4 grasses. Here, we report the assembly of the nuclear and chloroplast genomes of D. oligosanthes , from high-throughput short read sequencing data and a comparative transcriptomics analysis of the developing leaf of D. oligosanthes , S. viridis , and S. bicolor . Physiological and anatomical characterizations verified that D. oligosanthes utilizes the C 3 pathway for carbon fixation and lacks Kranz anatomy. Expression profiles of transcription factors along developing leaves of D. oligosanthes and S. viridis were compared with previously published data from S. bicolor , Zea mays , and Oryza sativa to identify a small suite of transcription factors that likely acquired functions specifically related to C 4 photosynthesis. In conclusion, the phylogenetic location of D. oligosanthes makes it an ideal C 3 plant for comparative analysis of C 4 evolution in the panicoid grasses. This genome will not only provide a better C 3 species for comparisons with C 4 panicoid grasses, but also highlights the power of using high-throughput sequencing to address questions in evolutionary biology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Measurement of the Activity Coefficients of P and Mn in Carbon-Saturated Fe-P-Mn-C Alloy

The thermodynamic properties of the Fe-P-Mn-C(sat.) alloy, which is obtained following the reduction of steelmaking slag or manganese ore, are not adequately clarified. Thus, the current study involved measuring the activity coefficients of both Mn and P in the alloy system. The Fe-P-Mn-C (sat.) alloy (2.5 to 15.2 mass pct of P and 2.9 to 12.8 mass pct of Mn) was equilibrated with Ag in a graphite crucible at 1673 K, and thus several thermodynamic data were obtained as follows: Interaction parameters: ε{sub Mn (C sat.)}{sup P}=− 4.72±0.27,(X{sub Mn}<0.06, X{sub P}<0.25, 1673K), ε{sub C (C sat.)}{sup P}=6.09 ± 0.15, (X{sub Mn}<0.06, X{sub P}<0.25, 1673K). C solubility: X{sub C[in Fe-P-Mn-C(sat.)]}=0.19e{sup −(6.09X{sub P}− 0.47X{sub M}{sub n})}. Activity coefficient: lnγ{sub Mn [in Fe-P-Mn-C(sat.)]}=− 4.72X{sub P}−0.47X{sub C}−0.87, lnγ{sub P [in Fe-P-Mn-C(sat.)]}{sup H}−lnγ{sub P [in Fe-P-C]}{sup H}=ε{sub P}{sup Mn}X{sub Mn}=−4.72X{sub Mn}, and lnγ{sub P [in Fe-P-Mn-C (sat.)]}{sup H}=−4.72X{sub Mn}+4.26X{sub P}+6.09X{sub C}. In addition, a comparison with the results obtained by previous studies on the selective reduction of steelmaking slag indicated that the activity coefficients of P and Mn obtained in the study were applicable.

36 MATERIALS SCIENCE↗
DOE OSTI2018

c-Myc-driven glycolysis via TXNIP suppression is dependent on glutaminase-MondoA axis in prostate cancer

Highlights: • c-Myc suppresses TXNIP transcription in a glutamine-dependent manner. • c-Myc induction of GLS1 is necessary for TXNIP suppression. • TXNIP represses glycolytic target genes broadly in c-Myc-driven cancers. • c-Myc and TXNIP levels are negatively associated in PCA tissues and predict patient outcome. Oncogenic c-Myc-induced metabolic reprogramming triggers cellular dependency on exogenous glucose and glutamine. Understanding how nutrients are used may provide new target for therapeutic intervention. We previously provided an alternate route to c-Myc-driven glucose metabolism via the repression of thioredoxin-interacting protein (TXNIP), which is a potent negative regulator of glucose uptake. Herein, we demonstrate that c-Myc suppression of TXNIP is predominantly through the activation of glutaminolysis via glutaminase (GLS1) in prostate cancer cells. Glutamine depletion blocked c-Myc-dependent reductions of TXNIP and its principal regulator MondoA transcriptional activity. Further, GLS1 inhibition by either siRNA or CB-839 resumed TXNIP expression that was repressed by c-Myc. The TXNIP promoter with mutant E-Box region, which was recognized by MondoA, failed to respond to c-Myc or GLS1, indicating c-Myc repression of TXNIP by GLS1 is predominantly through the blockage of MondoA activity. Especially, ectopic TXNIP expression decreased c-Myc-induce glucose uptake and lead to a broad range of glycolytic target gene suppressions. Thus TXNIP is a key adaptor for c-Myc-driven aerobic glycolysis. Supporting the biological significance of c-Myc and TXNIP, their reciprocal relationship are correlates with patient outcome and contributes to the aggressive phenotype in PCAs.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Dual-atom active sites embedded in two-dimensional C 2 N for efficient CO 2 electroreduction: A computational study

Double-atom catalysts (DACs) have emerged as an enhanced platform of single-atom catalyst for promoting electrocatalytic CO 2 reduction reaction (CO 2 RR). Herein, we present a density-functional theory study on CO 2 RR performance of seven C 2 N-supported homo- and heteronuclear DACs, denoted as M 2 @C 2 N. Our results demonstrate that there exists substantial synergistic effect of dual-metal-atom N 2 M 2 N 2 active site and C 2 N matrix on O&#x2550 C &#x2550O bond activation. The dual-atom M 2 sites are able to drive CO 2 RR beyond C 1 products with low limiting potential (U L ). Specifically, C 2 H 4 formation is preferred on FeM@C 2 N (M = Fe, Co, Ni, Cu) versus CH 4 formation on CuM@C 2 N (M = Co, Ni, Cu). Furthermore, *CO+*CO co-binding strength can serve as a descriptor for CO 2 RR activity for making C 2 products such that the moderate binding results in the lowest U L . Remarkably, C-affinity matters most to C—C bond coupling and C 2 H 4 formation while both C- and O-affinity control CH 4 formation. Furthermore, our results provide theoretical insight into rational design of DACs for efficient CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Enhanced performance of dye-sensitized solar cells based on organic dopant incorporated PVDF-HFP/PEO polymer blend electrolyte with g-C{sub 3}N{sub 4}/TiO{sub 2} photoanode

This work describes the effect of 2-aminopyrimidine (2-APY) on poly(vinylidinefluoride-co-hexafluoropropylene) (PVDF-HFP)/polyethylene oxide (PEO) blend polymer electrolyte along with binary iodide salts (tetrabutylammonium iodide (TBAI) and potassium iodide (KI)) and iodine (I{sub 2}) were studied for enhancing the efficiency of the dye-sensitized solar cells (DSSCs) consisting of g-C{sub 3}N{sub 4}/TiO{sub 2} composite as photoanode. The g-C{sub 3}N{sub 4} was synthesized from low cost urea by thermal condensation method. It was used as a precursor to synthesize the various weight percentage ratios (5%, 10% and 15%) of g-C{sub 3}N{sub 4}/TiO{sub 2} composites by wet-impregnation method. The pure and 2-APY incorporated PVDF-HFP/PEO polymer blend electrolytes were arranged by wet chemical process (casting method) using DMF as a solvent. The synthesized g-C{sub 3}N{sub 4}/TiO{sub 2} composites and polymer blend electrolytes were studied and analyzed by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometer (XRD) and scanning electron microscopy (SEM). The ionic conductivity values of the pure and 2-APY incorporated PVDF-HFP/PEO blend electrolytes were estimated to be 4.53×10{sup −5} and 1.87×10{sup −4} Scm{sup −1} respectively. The UV–vis absorption spectroscopy was carried out for the pure and different wt% of g-C{sub 3}N{sub 4}/TiO{sub 2} composites coated FTO films after N3 dye-sensitization. The 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} composite film showed a maximum absorption compared to the others. The DSSC assembled with 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} as photoanode using the pure polymer blend electrolyte exhibited a power conversion efficiency (PCE) of 3.17% , which was superior than that of DSSC based pure TiO{sub 2} (2.46%). However, the PCE was increased to 4.73% for the DSSC assembled using 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} as photoanode with 2-APY incorporated polymer blend electrolyte. Hence, the present study is a successful attempt to provide a new pathway to enhance the performance of DSSCs. - Graphical abstract: In this study, the g-C{sub 3}N{sub 4} was synthesized from low cost urea and it was used as a precursor to synthesize of g-C{sub 3}N{sub 4}/TiO{sub 2} composite. The pure and 2-APY incorporated PVDF-HFP/PEO electrolytes were fabricated by solution casting method. A remarkably enhanced PCE of 4.73% was observed for 2-APY incorporated PVDF-HFP/PEO electrolyte with g-C{sub 3}N{sub 4}/TiO{sub 2} composite photoanode based DSSC. - Highlights: • 2-APY added PVDF-HFP/PEO electrolyte was prepared by solution casting method. • The g-C{sub 3}N{sub 4}/TiO{sub 2} composites were synthesized by wet-impregnation method. • DSSC with g-C{sub 3}N{sub 4}/TiO{sub 2} and 2-APY added electrolyte showed the efficiency of 4.73 %. • The g-C{sub 3}N{sub 4} and 2-APY can be a useful dopant to enhance the performance of DSSCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Investigation of Laser-Induced Breakdown Spectroscopy and Multivariate Analysis for Differentiating Inorganic and Organic C in a Variety of Soils

Laser-induced breakdown spectroscopy (LIBS) along with multivariate analysis was used to differentiate between the total carbon (C), inorganic C, and organic C in a set of 58 different soils from 5 soil orders. A 532 nm laser with 45 mJ of laser power was used to excite the 58 samples of soil and the emission of all the elements present in the soil samples was recorded in a single spectrum with a wide wavelength range of 200–800 nm. The results were compared to the laboratory standard technique, e.g., combustion on a LECO-CN analyzer, to determine the true values for total C, inorganic C, and organic C concentrations. Our objectives were: 1) to determine the characteristic spectra of soils containing different amounts of organic and inorganic C, and 2) to examine the viability of this technique for differentiating between soils that contain predominantly organic and/or inorganic C content for a range of diverse soils. Previous work has shown that LIBS is an accurate and reliable approach to measuring total carbon content of soils, but it remains uncertain whether inorganic and organic forms of carbon can be separated using this approach. Total C and inorganic C exhibited correlation with rock-forming elements such as Al, Si, Fe, Ti, Ca, and Sr, while organic C exhibited minor correlation with these elements and a major correlation with Mg. We calculated a figure of merit (Mg/Ca) based on our results to enable differentiation between inorganic versus organic C. We obtained the LIBS validation prediction for total, inorganic, and organic C to have a coefficient of regression, r2 = 0.91, 0.87, and 0.91 respectively. These examples demonstrate an advance in LIBS-based techniques to distinguish between organic and inorganic C using the full wavelength spectra.

Martin, Madhavi Z.↗
DOE OSTI2020

Reaction Energetics and 13 C Fractionation of Alanine Transamination in the Aqueous and Gas Phases

The alanine transaminase enzyme catalyzes the transfer of an amino group from alanine to α-ketoglutarate to produce pyruvate and glutamate. Isotope fractionation factors (IFFs) for the reaction +H 3 NCH(CH 3 )COO – + – OOCCH 2 CH 2 C(O)COO – ↔ CH 3 C(O)COO – + + H 3 NCH(CH 2 CH 2 COO – )COO – (zwitterionic neutral alanine + doubly deprotonated α-ketoglutarate ↔ pyruvate + zwitterionic glutamate anion) were calculated from the partition functions of explicitly and implicitly solvated molecules at 298 K. Calculations were done for alanine (noncharge separated, zwitterion, deprotonated), pyruvic acid (neutral, deprotonated), glutamic acid (noncharge separated, zwitterion, deprotonated, doubly deprotonated), and α-ketoglutaric acid (neutral, deprotonated, doubly deprotonated). The computational results, calculated from gas phase- and aqueous-optimized clusters with explicit H 2 O molecules at the MP2/aug-cc-pVDZ and MP2/aug-cc-pVDZ/COSMO levels, respectively, predict that substitution of 13 C at the C2 position of alanine and pyruvic acid and their various forms leads to the C2 position of pyruvic acid/pyruvate being enriched in 13 C/ 12 C ratio by 9‰. Simpler approaches that estimate the IFFs based solely on changes in the zero-point energies (ZPEs) are consistent with the higher-level model. ZPE-based IFFs calculated for simple analogues formaldehyde and methylamine (analogous to the C2 positions of pyruvate and alanine, respectively) predict a 13 C enrichment in formaldehyde of 7–8‰ at the MP2/aug-cc-pVDZ and aug-cc-pVTZ levels. A simple predictive model using canonical functional group frequencies and reduced masses for 13 C exchange between R 2 C=O and R 2 CH–NH 2 predicted enrichment in R 2 C=O that is too large by a factor of two but is qualitatively accurate compared with the more sophisticated models. Our models are all in agreement with the expectation that pyruvate and formaldehyde will be preferentially enriched in 13 C because of the strength of their >C=O bond relative to that of ≡C–NH 2 in alanine and methylamine. 13 C/ 12 C substitution is also modeled at the methyl and carboxylic acid sites of alanine and pyruvic acid, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

C–H Activation of Pyrazolyl Ligands by Ru(II)

Previously, hydridotris(pyrazolyl)borate (Tp) Ru(II) alkyl and aryl complexes of the type TpRu(L)(NCMe)R (R = methyl or aryl; L = charge-neutral two-electron donating ligand) were demonstrated to activate aromatic C–H bonds. To confirm the impact of replacing the anionic Tp ligand with charge-neutral poly(pyrazolyl)alkane ligands, [(C(pz) 4 )Ru(P(OCH 2 ) 3 CEt)(NCMe)Me][BAr' 4 ] (pz = pyrazolyl, BAr' 4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) was prepared. Heating a C 6 D 6 solution of [(C(pz) 4 )Ru(P(OCH 2 ) 3 CEt)(NCMe)Me][BAr' 4 ] with 1 equiv of NCMe resulted in C–H activation of the 5-position of a pyrazolyl ring to yield [(κ 3 -( N , C 5 , N )C(pz) 4 )Ru(P(OCH 2 ) 3 CEt)(NCMe) 2 ][BAr' 4 ] and CH 4 . Intramolecular C–H activation of the 5-position of a pyrazolyl ring also occurred when (η 6 - p -cymene)Ru(P(OCH 2 ) 3 CEt)(Br)Ph was heated in the presence of C(pz) 4 to yield [(κ 3 - N , C 5 , N )C(pz) 4 ]Ru(P(OCH 2 ) 3 CEt)(NCMe)Br and C 6 H 6 . Density functional theory calculations showed that the different reactivities of TpRu(P(OCH 2 ) 3 CEt)(NCMe)R and [(C(pz) 4 )Ru(P(OCH 2 ) 3 CEt)(NCMe)Me][BAr' 4 ] result from the stronger binding of the Tp pyrazolyl rings to Ru(II) compared to that of C(pz) 4

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH₄ Reactions on Pd Catalysts

Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH₄ react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to Habstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cationlattice oxygen pairs (Pd 2+ -O 2- ) in PdO. The charges in the CH₃ and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*- covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd 2+ -O 2- pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H₃C···Pd···H)‡ transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3 •···*OH)‡ that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd 2+ and vicinal O 2- , Pd ox -O ox, cleave C-H bonds heterolytically via σ-bond metathesis, with Pd 2+ adding to the C-H bond, while O 2- abstracts the H-atom to form a four-center (H 3 C δ- ···Pd ox ···H δ+ ···O ox ) transition state without detectable Pdox reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH₄ oxidation turnover rates at oxygen chemical potentials leading to Pd to PdO transitions. These distinct mechanistic pathways for C-H bond activation, inferred from theory and experiment, resemble those prevalent on organometallic complexes. Metal centers present on surfaces as well as in homogeneous complexes act as both nucleophile and electrophile in oxidative additions, ligands (e.g., O* on surfaces) abstract H-atoms via reductive deprotonation of C-H bonds, and metal-ligand pairs, with the pair as electrophile and the metal as nucleophile, mediate σ-bond metathesis pathways.

Environmental Molecular Sciences Laboratory↗
NASA NTRS2000

Prostaglandin E2-induced up-regulation of c-fos messenger ribonucleic acid is primarily mediated by 3',5'-cyclic adenosine monophosphate in MC3T3-E1 osteoblasts

The mechanism by which the proto-oncogene, c-fos, is up-regulated in response to PGE2 in the mouse osteoblastic (MC3T3-E1) cell line was investigated using RT-PCR. c-fos messenger RNA up-regulation by dmPGE2 is rapid, starting 10 min post stimulation, and transient. The specific protein kinase A (PKA) inhibitor, H89, inhibited c-fos induction. Moreover, down-regulation of protein kinase C (PKC) activity by chronic TPA treatment had no effect on the induction of c-fos by dmPGE2. We conclude that up-regulation of c-fos by dmPGE2 is primarily dependent on PKA in MC3T3-E1 osteoblasts. In S49 lymphoma wild-type but not S49 cyc- cells, which are deficient in cAMP signaling, dmPGE2 up-regulates c-fos and increases cell growth compared with unstimulated cells. Thus in S49 lymphoma cells, c-fos induction by PGE2 is also dependent on cAMP signaling. The minimal c-fos promoter region required for dmPGE2-induced expression was identified by transfecting c-fos promoter deletion constructs coupled to the chloramphenicol acetyltransferase (CAT) reporter gene into Vero cells. Transfection of a plasmid containing 99 bp c-fos proximal promoter was sufficient to direct c-fos/CAT expression following stimulation with dmPGE2. Because induction of c-fos is mediated by cAMP, these data are consistent with activation of c-fos via the CRE/ATF cis element.

NASA Discipline Cell Biology↗
NASA NTRS2006

A Model-based Interpretation of Low-frequency Changes in the Carbon Cycle during the Last 120,000 years and its Implications for the Reconstruction of Atmospheric (delta) 14-C

A main caveat in the interpretation of observed changes in atmospheric (Delta)C-l4 during the last 50,000 years is the unknown variability of the carbon cycle, which together with changes in the C-14 production rates determines the C-14 dynamics. A plausible scenario explaining glacial/interglacial dynamics seen in atmospheric CO2 and (delta)C-13 was proposed recently (Kohler et al., 2005a). A similar approach that expands its interpretation to the C-14 cycle is an important step toward a deeper understanding of (Delta)C-14 variability. This approach is based on an ocean/atmosphere/biosphere box model of the global carbon cycle (BICYCLE) to reproduce low-frequency changes in atmospheric CO2 as seen in Antarctic ice cores. The model is forced forward in time by various paleoclimatic records derived from ice and sediment cores. The simulation results of our proposed scenario match a compiled CO2 record from various ice cores during the last 120,000 years with high accuracy (r(sup 2) = 0.89). We analyze scenarios with different C-14 production rates, which are either constant or based on Be-10 measured in Greenland ice cores or the recent high-resolution geomagnetic field reconstruction GLOPIS-75 and compare them with the available (Delta)C-14 data covering the last 50,000 years. Our results suggest that during the last glacial cycle in general less than 110%0o f the increased atmospheric (Delta)C-14 is based on variations in the carbon cycle, while the largest part (5/6) of the variations has to be explained by other factors. Glacial atmospheric (Delta)C-14 larger than 700% cannot not be explained within our framework, neither through carbon cycle-based changes nor through variable C-14 production. Superimposed on these general trends might lie positive anomalies in atmospheric (Delta)C-14 of approx. 50% caused by millennial-scale variability of the northern deep water production during Heinrich events and Dansgaard/Oeschger climate fluctuations. According to our model, the dominant processes that increase glacial (Delta)C-14 are a reduced glacial ocean circulation (+ approx.40%0), a restricted glacial gas exchange between the atmosphere and the surface ocean through sea ice coverage (+ approx. 20%), and the enrichment of dissolved inorganic carbon with C-14 in the surface waters through isotopic fractionation during higher glacial marine export production caused by iron fertilization (+ approx.10%).

Koehler, Peter↗
DOE OSTI2024

Observation of η c ( 2 S ) → K + K − η

By analyzing ( 27.12 ± 0.14 ) × 10 8 ψ ( 3686 ) events accumulated with the BESIII detector, the decay η c ( 2 S ) → K + K − η is observed for the first time with a significance of 6.2 σ after considering systematic uncertainties. The product of the branching fractions of ψ ( 3686 ) → γ η c ( 2 S ) and η c ( 2 S ) → K + K − η is measured to be B ( ψ ( 3686 ) → γ η c ( 2 S ) ) × B ( η c ( 2 S ) → K + K − η ) = ( 2.39 ± 0.32 ± 0.34 ) × 10 − 6 , where the first uncertainty is statistical, and the second one is systematic. The branching fraction of η c ( 2 S ) → K + K − η is determined to be B ( η c ( 2 S ) → K + K − η ) = ( 3.42 ± 0.46 ± 0.48 ± 2.44 ) × 10 − 3 , where the third uncertainty is due to the branching fraction of ψ ( 3686 ) → γ η c ( 2 S ) . Using a recent BESIII measurement of B ( η c ( 2 S ) → K + K − π 0 ) , we also determine the ratio between the branching fractions of η c ( 2 S ) → K + K − η and η c ( 2 S ) → K + K − π 0 to be 1.49 ± 0.22 ± 0.25 , which is consistent with the previous result of at a comparable precision level. Published by the American Physical Society 2024

Ablikim, M.↗