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1.
J Am Chem Soc ; 139(1): 47-50, 2017 01 11.
Artigo em Inglês | MEDLINE | ID: mdl-27958727

RESUMO

Electrochemical conversion of CO2 holds promise for utilization of CO2 as a carbon feedstock and for storage of intermittent renewable energy. Presently Cu is the only metallic electrocatalyst known to reduce CO2 to appreciable amounts of hydrocarbons, but often a wide range of products such as CO, HCOO-, and H2 are formed as well. Better catalysts that exhibit high activity and especially high selectivity for specific products are needed. Here a range of bimetallic Cu-Pd catalysts with ordered, disordered, and phase-separated atomic arrangements (Cuat:Pdat = 1:1), as well as two additional disordered arrangements (Cu3Pd and CuPd3 with Cuat:Pdat = 3:1 and 1:3), are studied to determine key factors needed to achieve high selectivity for C1 or C2 chemicals in CO2 reduction. When compared with the disordered and phase-separated CuPd catalysts, the ordered CuPd catalyst exhibits the highest selectivity for C1 products (>80%). The phase-separated CuPd and Cu3Pd achieve higher selectivity (>60%) for C2 chemicals than CuPd3 and ordered CuPd, which suggests that the probability of dimerization of C1 intermediates is higher on surfaces with neighboring Cu atoms. Based on surface valence band spectra, geometric effects rather than electronic effects seem to be key in determining the selectivity of bimetallic Cu-Pd catalysts. These results imply that selectivities to different products can be tuned by geometric arrangements. This insight may benefit the design of catalytic surfaces that further improve activity and selectivity for CO2 reduction.

2.
Nat Commun ; 7: 13869, 2016 12 13.
Artigo em Inglês | MEDLINE | ID: mdl-27958290

RESUMO

Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

3.
J Clin Lab Anal ; 30(6): 1061-1070, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27132877

RESUMO

BACKGROUND: Despite recent advances in the investigation of myeloproliferative neoplasms (MPN), the impact of genetic heterogeneity on its molecular pathogenesis has not been fully elucidated. Thus, in this study, we aim to characterize the genetic complexity in Korean patients with polycythemia vera (PV) and essential thrombocythemia (ET). METHODS: We conducted association studies using 84 single-nucleotide polymorphisms (SNPs) in 229 patients (96 with PV and 133 with ET) and 170 controls. Further, whole-genome sequencing was performed in six patients (two with JAK2 V617F and four with wild-type JAK2), and putative somatic mutations were validated in a further 69 ET patients. Clinical and laboratory characteristics were also analyzed. RESULTS: Several germline SNPs and the 46 haplotype were significantly associated with PV and ET. Three somatic mutations in MPDZ, IQCH, and CALR genes were selected and validated. The frequency of the CALR mutation was 58.0% (40/69) in ET patients, who did not carry JAK2/MPL mutations. Moreover, compared with JAK2 V617F-positive patients, those with CALR mutations showed lower hemoglobin and hematocrit levels (P = 0.004 and P = 0.002, respectively), higher platelet counts (P =0.008), and a lower frequency of cytoreductive therapy (P = 0.014). CONCLUSION: This study was the first comprehensive investigation of the genetic characteristics of Korean patients with PV and ET. We found that somatic mutations and the 46 haplotype contribute to PV and ET pathogenesis in Korean patients.


Assuntos
Predisposição Genética para Doença/genética , Janus Quinase 2/genética , Policitemia Vera/genética , Polimorfismo de Nucleotídeo Único/genética , Receptores de Trombopoetina/genética , Trombocitemia Essencial/genética , Adulto , Idoso , Idoso de 80 Anos ou mais , Proteínas de Transporte/genética , Análise Mutacional de DNA , Feminino , Frequência do Gene , Estudos de Associação Genética , Genótipo , Humanos , Masculino , Proteínas de Membrana , Pessoa de Meia-Idade , Policitemia Vera/epidemiologia , República da Coreia/epidemiologia , Estatísticas não Paramétricas , Trombocitemia Essencial/epidemiologia , Adulto Jovem
4.
PLoS One ; 11(1): e0143235, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-26799392

RESUMO

The presence of multiple variants for many mRNAs is a major contributor to protein diversity. The processing of these variants is tightly controlled in a cell-type specific manner and has a significant impact on gene expression control. Here we investigate the differential translation rates of individual mRNA variants in embryonic stem cells (ESCs) and in ESC derived Neural Precursor Cells (NPCs) using polysome profiling coupled to RNA sequencing. We show that there are a significant number of detectable mRNA variants in ESCs and NPCs and that many of them show variant specific translation rates. This is correlated with differences in the UTRs of the variants with the 5'UTR playing a predominant role. We suggest that mRNA variants that contain alternate UTRs are under different post-transcriptional controls. This is likely due to the presence or absence of miRNA and protein binding sites that regulate translation rate. This highlights the importance of addressing translation rate when using mRNA levels as a read out of protein abundance. Additional analysis shows that many annotated non-coding mRNAs are present on the polysome fractions in ESCs and NPCs. We believe that the use of polysome fractionation coupled to RNA sequencing is a useful method for analysis of the translation state of many different RNAs in the cell.


Assuntos
Células-Tronco Embrionárias/fisiologia , Biossíntese de Proteínas , RNA Mensageiro/genética , Regiões 3' não Traduzidas , Regiões 5' não Traduzidas , Animais , Diferenciação Celular , Células Cultivadas , Células-Tronco Embrionárias/citologia , Regulação da Expressão Gênica no Desenvolvimento , Fator de Crescimento Insulin-Like II/genética , Camundongos , Células-Tronco Neurais/fisiologia , Polirribossomos/genética , Polirribossomos/metabolismo , Splicing de RNA , Ribonucleoproteínas/genética , Análise de Sequência de RNA
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