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1.
Environ Sci Ecotechnol ; 22: 100474, 2024 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-39247805

RESUMO

Improving electrification feasibility is essential for reducing emissions from non-electric energy sources, thereby enhancing air quality and public health. Concurrently, climate mitigation actions, such as carbon pricing policies, have significant potential to alleviate increasing carbon dioxide (CO2) and other co-emitted air pollutants. However, the interactions between climate policy and the improvement of electrification feasibility at the provincial level remain unclear, collectively impacting the net-zero transition of energy-intensive sectors. Here we combine a technologically rich economic-energy-environment model with air quality modeling across China to examine the health, climate, and economic implications of large-scale upgrades in electrification feasibility and climate policies from 2017 to 2030. The results indicate that advancing electrification feasibility, coupled with adopting carbon pricing policies, is likely to facilitate a transition towards electricity-dominant energy systems. Improved electrification feasibility is projected to yield a 7-25% increase in nationwide climate benefits and a 5-14% increase in health benefits by 2030. These incremental benefits, coupled with reduced economic costs, result in a 22-68% increase in net benefits. However, regionally, improvements in electrification feasibility will lead to heightened power demand and unintended emissions from electric energy production in certain provinces (e.g., Nei Mongol) due to the coal-dominated power system. Additionally, in major coal-producing provinces like Shanxi and Shaanxi, enhanced electrification feasibility exacerbates the negative economic impacts of climate policies. This study provides quantitative insights into how improving electrification feasibility reshapes energy evolution and the benefit-cost profile of climate policy at the provincial level. The findings underscore the necessity of a well-designed compensation scheme between affected and unaffected provinces and coordinated emission mitigation across the power and other end-use sectors.

2.
Nat Mater ; 2024 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-39191981

RESUMO

Twist engineering has emerged as a powerful approach for modulating electronic properties in van der Waals heterostructures. While theoretical works have predicted the modulation of spin texture in graphene-based heterostructures by twist angle, experimental studies are lacking. Here, by performing spin precession experiments, we demonstrate tunability of the spin texture and associated spin-charge interconversion with twist angle in WSe2/graphene heterostructures. For specific twist angles, we detect a spin component radial with the electron's momentum, in addition to the standard orthogonal component. Our results show that the helicity of the spin texture can be reversed by twist angle, highlighting the critical role of the twist angle in the spin-orbit properties of WSe2/graphene heterostructures and paving the way for the development of spin-twistronic devices.

3.
Chem Res Toxicol ; 37(8): 1445-1452, 2024 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-39041427

RESUMO

Tandem lesions, which are defined by two or more contiguously damaged nucleotides, are a hallmark of ionizing radiation. Recently, tandem lesions containing 5-formyl-2'-deoxyuridine (5-fdU) flanked by a 5'-8-OxodGuo or Fapy•dG were discovered, and they are more mutagenic in human cells than the isolated lesions. In the current study, we examined replication of these tandem lesions in Escherichia coli. Bypass efficiency of both tandem lesions was reduced by 30-40% compared to the isolated lesions. Mutation frequencies (MFs) of isolated 8-OxodGuo and Fapy•dG were low, and no mutants were isolated from replication of a 5-fdU construct. The types of mutations from 8-OxodGuo were targeted G → T transversion, whereas Fapy•dG predominantly gave G → T and G deletion. 5'-8-OxodGuo-5-fdU also gave exclusively G → T mutation, which was 3-fold and 11-fold greater, without and with SOS induction, respectively, compared to that of an isolated 8-OxodGuo. In mutY/mutM cells, the MF of 8-OxodGuo and 5'-8-OxodGuo-5-fdU increased 13-fold and 7-fold, respectively. The MF of 5'-8-OxodGuo-5-fdU increased 2-fold and 3-fold in Pol II- and Pol IV-deficient cells, respectively, suggesting that these polymerases carry out largely error-free bypass. The MF of 5'- Fapy•dG-5-fdU was similar without (13 ± 1%) and with (16 ± 2%) SOS induction. Unlike the complex mutation spectrum reported earlier in human cells for 5'- Fapy•dG-5-fdU, with G → T as the major type of errors, in E. coli, the mutations were predominantly from deletion of 5-fdU. We postulate that removal of adenine-incorporated opposite 8-OxodGuo by Fpg and MutY repair proteins is partially impaired in the tandem 5'-8-OxodGuo-5-fdU, resulting in an increase in the G → T mutations, whereas a slippage mechanism may be operating in the 5'- Fapy•dG-5-fdU mutagenesis. This study showed that not only are these tandem lesions more mutagenic than the isolated lesions but they may also exhibit different types of mutations in different organisms.


Assuntos
8-Hidroxi-2'-Desoxiguanosina , Escherichia coli , Escherichia coli/efeitos dos fármacos , Escherichia coli/genética , 8-Hidroxi-2'-Desoxiguanosina/metabolismo , Desoxiuridina/análogos & derivados , Desoxiuridina/química , Desoxiuridina/farmacologia , Mutagênicos/toxicidade , Desoxiguanosina/análogos & derivados , Desoxiguanosina/metabolismo , Mutação , Mutagênese , Dano ao DNA
4.
J Org Chem ; 89(16): 11304-11322, 2024 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-39052894

RESUMO

The manuscript reports on 7-deazapurine and pyrimidine nucleoside and oligonucleotide cycloadducts formed by the inverse electron demand Diels-Alder (iEDDA) reaction with 3,6-di(pyrid-2-yl)-1,2,4,5-tetrazine. Cycloadducts were constructed from ethynylated and vinylated nucleobases. Oligonucleotides were synthesized containing iEDDA modifications, and the impact on duplex stability was investigated. iEDDA reactions were performed on nucleoside triple bond side chains. Oxidation was not required in these cases as dihydropyridazine intermediates are not formed. In contrast, oxidation is necessary for reactions performed on alkenyl compounds. This was verified on 5-vinyl-2'-deoxyuridine. A diastereomeric mixture of 1,2-dihydropyridazine cycloadduct intermediates was isolated, characterized, and later oxidized. 12-mer oligonucleotides containing 1,2-pyridazine inverse Diels-Alder cycloadducts and their precursors were hybridized to short DNA duplexes. For that, a series of phosphoramidites was prepared. DNA duplexes with 7-functionalized 7-deazaadenines and 5-functionalized pyrimidines display high duplex stability when spacer units are present between nucleobases and pyridazine cycloadducts. A direct connectivity of the pyridazine moiety to nucleobases as reported for metabolic labeling of vinyl nucleosides reduced duplex stability strongly. Oligonucleotides bearing linkers with and without pyridazine cycloadducts attached to the 7-deazaadenine nucleobase significantly reduced mismatch formation with dC and dG.


Assuntos
Pareamento de Bases , Reação de Cicloadição , Oligonucleotídeos , Piridazinas , Piridazinas/química , Oligonucleotídeos/química , Purinas/química , Estrutura Molecular , Nucleosídeos de Pirimidina/química , DNA/química , Pareamento Incorreto de Bases
5.
Nucleic Acids Res ; 52(9): 5392-5405, 2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38634780

RESUMO

N6-(2-deoxy-α,ß-d-erythro-pentofuranosyl)-2,6-diamino-4-hydroxy-5-formamido-pyrimidine (Fapy•dG) is formed from a common intermediate and in comparable amounts to the well-studied mutagenic DNA lesion 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-OxodGuo). Fapy•dG preferentially gives rise to G → T transversions and G → A transitions. However, the molecular basis by which Fapy•dG is processed by DNA polymerases during this mutagenic process remains poorly understood. To address this we investigated how DNA polymerase ß (Pol ß), a model mammalian polymerase, bypasses a templating Fapy•dG, inserts Fapy•dGTP, and extends from Fapy•dG at the primer terminus. When Fapy•dG is present in the template, Pol ß incorporates TMP less efficiently than either dCMP or dAMP. Kinetic analysis revealed that Fapy•dGTP is a poor substrate but is incorporated ∼3-times more efficiently opposite dA than dC. Extension from Fapy•dG at the 3'-terminus of a nascent primer is inefficient due to the primer terminus being poorly positioned for catalysis. Together these data indicate that mutagenic bypass of Fapy•dG is likely to be the source of the mutagenic effects of the lesion and not Fapy•dGTP. These experiments increase our understanding of the promutagenic effects of Fapy•dG.


Assuntos
DNA Polimerase beta , Replicação do DNA , Formamidas , Furanos , Pirimidinas , Humanos , Cristalografia por Raios X , DNA/química , DNA/metabolismo , DNA Polimerase beta/metabolismo , DNA Polimerase beta/química , Cinética , Modelos Moleculares , Pirimidinas/química , Pirimidinas/metabolismo , Furanos/química , Furanos/metabolismo , Formamidas/metabolismo , Mutagênese
6.
bioRxiv ; 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38293220

RESUMO

N6-(2-deoxy-α,ß-D-erythro-pentofuranosyl)-2,6-diamino-4-hydroxy-5-formamido-pyrimidine (Fapy•dG) is formed from a common intermediate and in comparable amounts to the well-studied mutagenic DNA lesion 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-OxodGuo). Fapy•dG preferentially gives rise to G → T transversions and G → A transitions. However, the molecular basis by which Fapy•dG is processed by DNA polymerases during this mutagenic process remains poorly understood. To address this we investigated how DNA polymerase ß (Pol ß), a model mammalian polymerase, bypasses a templating Fapy•dG, inserts Fapy•dGTP, and extends from Fapy•dG at the primer terminus. When Fapy•dG is present in the template, Pol ß incorporates TMP less efficiently than either dCMP or dAMP. Kinetic analysis revealed that Fapy•dGTP is a poor substrate but is incorporated ∼3-times more efficiently opposite dA than dC. Extension from Fapy•dG at the 3'-terminus of a nascent primer is inefficient due to the primer terminus being poorly positioned for catalysis. Together these data indicate that mutagenic bypass of Fapy•dG is likely to be the source of the mutagenic effects of the lesion and not Fapy•dGTP. These experiments increase our understanding of the promutagenic effects of Fapy•dG.

7.
Adv Mater ; 36(18): e2310768, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38237911

RESUMO

A charge density wave (CDW) represents an exotic state in which electrons are arranged in a long-range ordered pattern in low-dimensional materials. Although the understanding of the fundamental character of CDW is enriched after extensive studies, its practical application remains limited. Here, an unprecedented demonstration of a tunable charge-spin interconversion (CSI) in graphene/1T-TaS2 van der Waals heterostructures is shown by manipulating the distinct CDW phases in 1T-TaS2. Whereas CSI from spins polarized in all three directions is observed in the heterostructure when the CDW phase does not show commensurability, the output of one of the components disappears, and the other two are enhanced when the CDW phase becomes commensurate. The experimental observation is supported by first-principles calculations, which evidence that chiral CDW multidomains in the heterostructure are at the origin of the switching of CSI. The results uncover a new approach for on-demand CSI in low-dimensional systems, paving the way for advanced spin-orbitronic devices.

8.
Nat Commun ; 14(1): 8350, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-38102120

RESUMO

The transition to low-carbon electricity is crucial for meeting global climate goals. However, given the uneven spatial distribution and temporal variability of renewable resources, balancing the supply and demand of electricity will be challenging when relying on close to 100% shares of renewable energy. Here, we use an electricity planning model with hourly supply-demand projections and high-resolution renewable resource maps, to examine whether transcontinental power pools reliably meet the growing global demand for renewable electricity and reduce the system cost. If all suitable sites for renewable energy are available for development, transcontinental trade in electricity reduces the annual system cost of electricity in 2050 by 5-52% across six transcontinental power pools compared to no electricity trade. Under land constraints, if only the global top 10% of suitable renewable energy sites are available, then without international trade, renewables are unable to meet 12% of global demand in 2050. Introducing transcontinental power pools with the same land constraints, however, enables renewables to meet 100% of future electricity demand, while also reducing costs by up to 23% across power pools. Our results highlight the benefits of expanding regional transmission networks in highly decarbonized but land-constrained future electricity systems.

9.
Nat Commun ; 14(1): 7253, 2023 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-37945570

RESUMO

Two-dimensional magnets and superconductors are emerging as tunable building-blocks for quantum computing and superconducting spintronic devices, and have been used to fabricate all two-dimensional versions of traditional devices, such as Josephson junctions. However, novel devices enabled by unique features of two-dimensional materials have not yet been demonstrated. Here, we present NbSe2/CrSBr van der Waals superconducting spin valves that exhibit infinite magnetoresistance and nonreciprocal charge transport. These responses arise from a unique metamagnetic transition in CrSBr, which controls the presence of localized stray fields suitably oriented to suppress the NbSe2 superconductivity in nanoscale regions and to break time reversal symmetry. Moreover, by integrating different CrSBr crystals in a lateral heterostructure, we demonstrate a superconductive spin valve characterized by multiple stable resistance states. Our results show how the unique physical properties of layered materials enable the realization of high-performance quantum devices based on novel working principles.

10.
DNA Repair (Amst) ; 129: 103527, 2023 09.
Artigo em Inglês | MEDLINE | ID: mdl-37467631

RESUMO

Modified nucleotides often hinder and/or decrease the fidelity of DNA polymerases. Tandem lesions, which are comprised of DNA modifications at two contiguous nucleotide positions, can be even more detrimental to genome stability. Recently, tandem lesions containing 5-formyl-2'-deoxyuridine (5fdU) flanked at the 5'-position by 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-OxodGuo) or N-(2-deoxy-α,ß-D-erythropentofuranosyl)-N-(2,6-diamino-4-hydroxy-5-formamidopyrimidine (Fapy•dG) were discovered. We examined the replication of 5'- 8-OxodGuo-5fdU and 5'-Fapy•dG-5fdU tandem lesions in HEK 293T cells and several polymerase deficient variants by transfecting single-stranded vectors containing them. The local sequence of the tandem lesions encompasses the 273 codon of the p53 gene, a mutational hot-spot. The bypass efficiency and mutation spectra of the tandem lesions were compared to those of the isolated lesions. Replication of weakly mutagenic 5-fdU is little changed when part of the 5'- 8-OxodGuo-5fdU tandem lesion. G → T transversions attributable to 8-OxodGuo increase > 10-fold when the tandem lesion is bypassed. 5'-Fapy•dG-5fdU has a synergistic effect on the error-prone bypass of both lesions. The mutation frequency (MF) of 5'-Fapy•dG-5fdU increases 3-fold compared to isolated Fapy•dG. In addition, a 5'-adjacent Fapy•dG significantly increases the MF of 5fdU. The major mutation, G → T transversions, decrease by almost a third in hPol κ- cells, which is the opposite effect when isolated Fapy•dG in the same sequence context is replicated in HEK 293T cells in the same sequence. Steady-state kinetics indicate that hPol κ contributes to greater G → T transversions by decreasing the specificity constant for dCTP compared to an isolated Fapy•dG. The greater conformational freedom of Fapy•dG compared to 8-OxodGuo and its unusual ability to epimerize at the anomeric center is believed to be the source of the complex effects of 5'-Fapy•dG-5fdU on replication.


Assuntos
DNA Polimerase Dirigida por DNA , Mutagênicos , Humanos , 8-Hidroxi-2'-Desoxiguanosina , Mutagênese , Nucleotídeos , Desoxiguanosina , Dano ao DNA
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