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1.
Autophagy ; : 1-18, 2024 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-38964379

RESUMO

Macroautophagic/autophagic and endocytic pathways play essential roles in maintaining homeostasis at different levels. It remains poorly understood how both pathways are coordinated and fine-tuned for proper lysosomal degradation of diverse cargoes. We and others recently identified a Golgi-resident RAB GTPase, RAB2A, as a positive regulator that controls both autophagic and endocytic pathways. In the current study, we report that TBC1D4 (TBC1 domain family member 4), a TBC domain-containing protein that plays essential roles in glucose homeostasis, suppresses RAB2A-mediated autophagic and endocytic pathways. TBC1D4 bound to RAB2A through its N-terminal PTB2 domain, which impaired RAB2A-mediated autophagy at the early stage by preventing ULK1 complex activation. During the late stage of autophagy, TBC1D4 impeded the association of RUBCNL/PACER and RAB2A with STX17 on autophagosomes by direct interaction with RUBCNL via its N-terminal PTB1 domain. Disruption of the autophagosomal trimeric complex containing RAB2A, RUBCNL and STX17 resulted in defective HOPS recruitment and eventually abortive autophagosome-lysosome fusion. Furthermore, TBC1D4 inhibited RAB2A-mediated endocytic degradation independent of RUBCNL. Therefore, TBC1D4 and RAB2A form a dual molecular switch to modulate autophagic and endocytic pathways. Importantly, hepatocyte- or adipocyte-specific tbc1d4 knockout in mice led to elevated autophagic flux and endocytic degradation and tissue damage. Together, this work establishes TBC1D4 as a critical molecular brake in autophagic and endocytic pathways, providing further mechanistic insights into how these pathways are intertwined both in vitro and in vivo.Abbreviations: ACTB: actin beta; ATG9: autophagy related 9; ATG14: autophagy related 14; ATG16L1: autophagy related 16 like 1; CLEM: correlative light electron microscopy; Ctrl: control; DMSO: dimethyl sulfoxide; EGF: epidermal growth factor; EGFR: epidermal growth factor receptor; FL: full length; GAP: GTPase-activating protein; GFP: green fluorescent protein; HOPS: homotypic fusion and protein sorting; IP: immunoprecipitation; KD: knockdown; KO: knockout; LAMP1: lysosomal associated membrane protein 1; MAP1LC3B/LC3B: microtubule associated protein 1 light chain 3 beta; OE: overexpression; PG: phagophore; PtdIns3K: class III phosphatidylinositol 3-kinase; SLC2A4/GLUT4: solute carrier family 2 member 4; SQSTM1/p62: sequestosome 1; RUBCNL/PACER: rubicon like autophagy enhancer; STX17: syntaxin 17; TAP: tandem affinity purification; TBA: total bile acid; TBC1D4: TBC1 domain family member 4; TUBA1B: tubulin alpha 1b; ULK1: unc-51 like autophagy activating kinase 1; VPS39: VPS39 subunit of HOPS complex; WB: western blot; WT: wild type.

2.
J Phys Chem Lett ; 15(28): 7244-7253, 2024 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-38976358

RESUMO

Conical intersections (CIs) are pivotal in many photochemical processes. Traditional quantum chemistry methods, such as the state-average multiconfigurational methods, face computational hurdles in solving the electronic Schrödinger equation within the active space on classical computers. While quantum computing offers a potential solution, its feasibility in studying CIs, particularly on real quantum hardware, remains largely unexplored. Here, we present the first successful realization of a hybrid quantum-classical state-average complete active space self-consistent field method based on the variational quantum eigensolver (VQE-SA-CASSCF) on a superconducting quantum processor. This approach is applied to investigate CIs in two prototypical systems─ethylene (C2H4) and triatomic hydrogen (H3). We illustrate that VQE-SA-CASSCF, coupled with ongoing hardware and algorithmic enhancements, can lead to a correct description of CIs on existing quantum devices. These results lay the groundwork for exploring the potential of quantum computing to study CIs in more complex systems in the future.

3.
Angew Chem Int Ed Engl ; : e202409001, 2024 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-38990826

RESUMO

Formic acid (FA) dehydrogenation and CO2 hydrogenation to FA/formate represent promising methodologies for the efficient and clean storage and release of hydrogen, forming a CO2-neutral energy cycle. Here, we report the synthesis of highly dispersed and stable bimetallic Pd-based nanoparticles, immobilized on self-pillared silicalite-1 (SP-S-1) zeolite nanosheets using an incipient wetness co-impregnation technique. Owing to the highly accessible active sites, effective mass transfer, exceptional hydrophilicity, and the synergistic effect of the bimetallic species, the optimized PdCe0.2/SP-S-1 catalyst demonstrated unparalleled catalytic performance in both FA dehydrogenation and CO2 hydrogenation to formate. Remarkably, it achieved a hydrogen generation rate of 5974 molH2 molPd-1 h-1 and a formate production rate of 536 molformate molPd-1 h-1 at 50 °C, surpassing most previously reported heterogeneous catalysts under similar conditions. Density functional theory calculations reveal that the interfacial effect between Pd and cerium oxide clusters substantially reduces the activation barriers for both reactions, thereby increasing the catalytic performance. Our research not only showcases a compelling application of zeolite nanosheet-supported bimetallic nanocatalysts in CO2-mediated hydrogen storage and release but also contributes valuable insights towards the development of safe, efficient, and sustainable hydrogen technologies.

4.
Nat Cell Biol ; 26(7): 1077-1092, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38926505

RESUMO

Cargo translocation across membranes is a crucial aspect of secretion. In conventional secretion signal peptide-equipped proteins enter the endoplasmic reticulum (ER), whereas a subset of cargo lacking signal peptides translocate into the ER-Golgi intermediate compartment (ERGIC) in a process called unconventional protein secretion (UcPS). The regulatory events at the ERGIC in UcPS are unclear. Here we reveal the involvement of ERGIC-localized small GTPases, Rab1 (Rab1A and Rab1B) and Rab2A, in regulating UcPS cargo transport via TMED10 on the ERGIC. Rab1 enhances TMED10 translocator activity, promoting cargo translocation into the ERGIC, whereas Rab2A, in collaboration with KIF5B, regulates ERGIC compartmentalization, establishing a UcPS-specific compartment. This study highlights the pivotal role of ERGIC-localized Rabs in governing cargo translocation and specifying the ERGIC's function in UcPS.


Assuntos
Retículo Endoplasmático , Complexo de Golgi , Transporte Proteico , Retículo Endoplasmático/metabolismo , Humanos , Complexo de Golgi/metabolismo , Células HeLa , Cinesinas/metabolismo , Cinesinas/genética , Células HEK293 , Translocador Nuclear Receptor Aril Hidrocarboneto/metabolismo , Translocador Nuclear Receptor Aril Hidrocarboneto/genética , Proteínas rab de Ligação ao GTP/metabolismo , Proteínas rab de Ligação ao GTP/genética , Proteínas de Membrana/metabolismo , Proteínas de Membrana/genética , Animais , Proteínas rab1 de Ligação ao GTP/metabolismo , Proteínas rab1 de Ligação ao GTP/genética
5.
Small Methods ; : e2400376, 2024 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-38801007

RESUMO

Ammonia borane (AB) has emerged as a promising chemical hydrogen storage material. The development of efficient, stable, and cost-effective catalysts for AB hydrolysis is the key to achieving hydrogen energy economy. Here, cobalt phosphide (CoP) is used to anchor single-atom Pt species, acting as robust catalysts for hydrogen generation from AB hydrolysis. Thanks to the high Pt utilization and the synergy between CoP and Pt species, the optimized Pt/CoP-100 catalyst exhibits an unprecedented hydrogen generation rate, giving a record turnover frequency (TOF) value of 39911 mo l H 2 mo l Pt - 1 mi n - 1 ${\mathrm{mo}}{{{\mathrm{l}}}_{{{{\mathrm{H}}}_{\mathrm{2}}}}}{\mathrm{\ mo}}{{{\mathrm{l}}}_{{\mathrm{Pt}}}}^{{\mathrm{ - 1}}}{\mathrm{\ mi}}{{{\mathrm{n}}}^{{\mathrm{ - 1}}}}$ and turnover number of 2926829 mo l H 2 mo l Pt - 1 ${\mathrm{mo}}{{{\mathrm{l}}}_{{{{\mathrm{H}}}_{\mathrm{2}}}}}{\mathrm{\ mo}}{{{\mathrm{l}}}_{{\mathrm{Pt}}}}^{{\mathrm{ - 1}}}$ at room temperature. These metrics surpass those of all existing state-of-the-art supported metal catalysts by an order of magnitude. Density functional theory calculations reveal that the integration of single-atom Pt onto the CoP substrate significantly enhances adsorption and dissociation processes for both water and AB molecules, thereby facilitating hydrogen production from AB hydrolysis. Interestingly, the TOF value is further elevated to 54878 mo l H 2 mo l Pt - 1 mi n - 1 ${\mathrm{mo}}{{{\mathrm{l}}}_{{{{\mathrm{H}}}_{\mathrm{2}}}}}{\mathrm{\ mo}}{{{\mathrm{l}}}_{{\mathrm{Pt}}}}^{{\mathrm{ - 1}}}{\mathrm{\ mi}}{{{\mathrm{n}}}^{{\mathrm{ - 1}}}}$ under UV-vis light irradiation, which can be attributed to the efficient separation and mobility of photogenerated carriers at the Pt-CoP interface. The findings underscore the effectiveness of CoP as a support for single-atom metals in hydrogen production, offering insights for designing high-performance catalysts for chemical hydrogen storage.

6.
J Chem Phys ; 160(17)2024 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-38748029

RESUMO

Libcint is a library designed for the evaluation of analytical integrals for Gaussian type orbitals. It prioritizes simplicity, ease of use, and efficiency for the development of quantum chemistry programs. In the release of version 6.0, Libcint supports the computation of integrals for various operators, such as overlap, Coulomb, Gaunt, Breit, attenuated Coulomb, Slater-type geminals, and Yukawa potential, as well as arbitrary orders of derivatives for these operators. To enhance the usability of the library, Libcint provides a uniform function signature for all integral functions. A code generator is included to automate the implementation of new integrals. To achieve better performance on modern central processing unit architectures, the library employs explicit single instruction multiple data parallelization in the code implementation.

7.
Chem Asian J ; : e202400436, 2024 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-38753576

RESUMO

Prolonging the lifetime of SAPO-34 catalysts and enhancing their olefin selectivity in methanol-to-olefin (MTO) reactions are critical yet challenging objectives. Here, a series of hierarchical SAPO-34 catalysts were synthesized using a straightforward recrystallization method. The incorporation of triethylamine into the recrystallization mother liquor facilitated the formation of mesopores, achieving a high solid yield of up to 90%. Notably, the addition of phosphoric acid and ammonium polyvinyl phosphate alcohol during the recrystallization process significantly enhanced the crystallinity and regularity of the hierarchical SAPO-34 crystals, consequently increasing the mesopore size. Due to the substantially improved mass transfer efficiency and moderated acidity, the SP34-0.14P-0.06R catalysts exhibited a prolonged operational life of 344 min and 80.3% selectivity of ethylene and propylene at a WHSV of 2h-1. This performance markedly surpasses that of the parent SP34 catalyst, which demonstrated a lifetime of 136 min and a selectivity of 78.0%. Remarkably, the SP34-0.14P-0.06R maintained a lifetime of 166 minutes even at a high WHSV of 10h-1, which is more than 5-fold greater than that of the original microporous SP34. This research offers valuable insights into the design and development of hierarchically porous zeolites with high yields, enhancing the efficiency of MTO reactions and other applications.

8.
Autophagy ; 20(8): 1762-1779, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38597182

RESUMO

Non-structural protein 2 (nsp2) exists in all coronaviruses (CoVs), while its primary function in viral pathogenicity, is largely unclear. One such enteric CoV, porcine epidemic diarrhea virus (PEDV), causes high mortality in neonatal piglets worldwide. To determine the biological role of nsp2, we generated a PEDV mutant containing a complete nsp2 deletion (rPEDV-Δnsp2) from a highly pathogenic strain by reverse genetics, showing that nsp2 was dispensable for PEDV infection, while its deficiency reduced viral replication in vitro. Intriguingly, rPEDV-Δnsp2 was entirely avirulent in vivo, with significantly increased productions of IFNB (interferon beta) and IFN-stimulated genes (ISGs) in various intestinal tissues of challenged newborn piglets. Notably, nsp2 targets and degrades TBK1 (TANK binding kinase 1), the critical kinase in the innate immune response. Mechanistically, nsp2 induced the macroautophagy/autophagy process and recruited a selective autophagic receptor, NBR1 (NBR1 autophagy cargo receptor). NBR1 subsequently facilitated the K48-linked ubiquitination of TBK1 and delivered it for autophagosome-mediated degradation. Accordingly, the replication of rPEDV-Δnsp2 CoV was restrained by reduced autophagy and excess productions of type I IFNs and ISGs. Our data collectively define enteric CoV nsp2 as a novel virulence determinant, propose a crucial role of nsp2 in diminishing innate antiviral immunity by targeting TBK1 for NBR1-mediated selective autophagy, and pave the way to develop a new type of nsp2-based attenuated PEDV vaccine. The study also provides new insights into the prevention and treatment of other pathogenic CoVs.Abbreviations: 3-MA: 3-methyladenine; Baf A1: bafilomycin A1; CoV: coronavirus; CQ: chloroquine; dpi: days post-inoculation; DMVs: double-membrane vesicles; GABARAP: GABA type A receptor-associated protein; GFP: green fluorescent protein; GIGYF2: GRB10 interacting GYF protein 2; hpi: hours post-infection; IFA: immunofluorescence assay; IFIH1: interferon induced with helicase C domain 1; IFIT2: interferon induced protein with tetratricopeptide repeats 2; IFITM1: interferon induced transmembrane protein 1; IFNB: interferon beta; IRF3: interferon regulatory factor 3; ISGs: interferon-stimulated genes; mAb: monoclonal antibody; MAP1LC3/LC3: microtubule associated protein 1 light chain 3; MAVS: mitochondrial antiviral signaling protein; NBR1: NBR1 autophagy cargo receptor; nsp2: non-structural protein 2; OAS1: 2'-5'-oligoadenylate synthetase 1; PEDV: porcine epidemic diarrhea virus; PRRs: pattern recognition receptors; RIGI: RNA sensor RIG-I; RT-qPCR: reverse transcription quantitative polymerase chain reaction; SQSTM1: sequestosome 1; TBK1: TANK binding kinase 1; TCID50: 50% tissue culture infectious doses; VSV: vesicular stomatitis virus.


Assuntos
Autofagia , Imunidade Inata , Vírus da Diarreia Epidêmica Suína , Proteínas Serina-Treonina Quinases , Proteínas não Estruturais Virais , Replicação Viral , Animais , Proteínas não Estruturais Virais/metabolismo , Proteínas não Estruturais Virais/genética , Proteínas não Estruturais Virais/imunologia , Proteínas Serina-Treonina Quinases/metabolismo , Autofagia/genética , Suínos , Vírus da Diarreia Epidêmica Suína/patogenicidade , Vírus da Diarreia Epidêmica Suína/imunologia , Chlorocebus aethiops , Humanos , Virulência , Células Vero , Ubiquitinação , Infecções por Coronavirus/imunologia , Infecções por Coronavirus/virologia , Interferon beta/metabolismo , Fatores de Virulência/metabolismo , Fatores de Virulência/genética , Células HEK293
9.
Proc Natl Acad Sci U S A ; 121(11): e2316553121, 2024 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-38437553

RESUMO

Developing cost-effective and high-performance electrocatalysts for oxygen reduction reaction (ORR) is critical for clean energy generation. Here, we propose an approach to the synthesis of iron phthalocyanine nanotubes (FePc NTs) as a highly active and selective electrocatalyst for ORR. The performance is significantly superior to FePc in randomly aggregated and molecularly dispersed states, as well as the commercial Pt/C catalyst. When FePc NTs are anchored on graphene, the resulting architecture shifts the ORR potentials above the redox potentials of Fe2+/3+ sites. This does not obey the redox-mediated mechanism operative on conventional FePc with a Fe2+-N moiety serving as the active sites. Pourbaix analysis shows that the redox of Fe2+/3+ sites couples with HO- ions transfer, forming a HO-Fe3+-N moiety serving as the ORR active sites under the turnover condition. The chemisorption of ORR intermediates is appropriately weakened on the HO-Fe3+-N moiety compared to the Fe2+-N state and thus is intrinsically more ORR active.

10.
J Am Chem Soc ; 146(13): 8939-8948, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38526452

RESUMO

Propane dehydrogenation (PDH) reaction has emerged as one of the most promising propylene production routes due to its high selectivity for propylene and good economic benefits. However, the commercial PDH processes usually rely on expensive platinum-based and poisonous chromium oxide based catalysts. The exploration of cost-effective and ecofriendly PDH catalysts with excellent catalytic activity, propylene selectivity, and stability is of great significance yet remains challenging. Here, we discovered a new active center, i.e., an unsaturated tricoordinated cobalt unit (≡Si-O)CoO(O-Mo) in a molybdenum-doped silicalite-1 zeolite, which afforded an unprecedentedly high propylene formation rate of 22.6 molC3H6 gCo-1 h-1 and apparent rate coefficient of 130 molC3H6 gCo-1 h-1 bar-1 with >99% of propylene selectivity at 550 °C. Such activity is nearly one magnitude higher than that of previously reported Co-based catalysts in which cobalt atoms are commonly tetracoordinated, and even superior to that of most of Pt-based catalysts under similar operating conditions. Density functional theory calculations combined with the state-of-the-art characterizations unravel the role of the unsaturated tricoordinated Co unit in facilitating the C-H bond-breaking of propane and propylene desorption. The present work opens new opportunities for future large-scale industrial PDH production based on inexpensive non-noble metal catalysts.

11.
Autophagy ; 20(1): 210-211, 2024 01.
Artigo em Inglês | MEDLINE | ID: mdl-37651691

RESUMO

Reticulophagy is an evolutionarily conserved mechanism essential to maintain the endoplasmic reticulum (ER) homeostasis. A series of studies identified a panel of reticulophagy receptors. However, it remains unclear how these receptors sense upstream signals for spatiotemporal control of reticulophagy and how ER is fragmented into small pieces for sequestration into phagophores. Recently, we and others showed that the oligomerization of RETREG1/FAM134B (reticulophagy regulator 1), an reticulophagy receptor, triggers the scission of ER membrane to facilitate reticulophagy. Furthermore, we demonstrated that upstream signals are transduced by sequential phosphorylation and acetylation of RETREG1, which stimulate its oligomerization, ER fragmentation and reticulophagy. Our work provides further mechanistic insights into how reticulophagy receptor conveys cellular signals to fine-tune of ER homeostasis.Abbreviations: ER, endoplasmic reticulum; MAP1LC3, microtubule-associated protein light chain 3; RETREG1, reticulophagy regulator 1; RHD, reticulon-homology domain.


Assuntos
Autofagia , Retículo Endoplasmático , Retículo Endoplasmático/metabolismo , Autofagossomos/metabolismo , Estresse do Retículo Endoplasmático , Proteínas de Transporte/metabolismo , Proteínas Associadas aos Microtúbulos/metabolismo
12.
Autophagy ; 20(2): 221-241, 2024 02.
Artigo em Inglês | MEDLINE | ID: mdl-37700498

RESUMO

ABBREVIATIONS: ACOX1: acyl-CoA oxidase 1; ADH5: alcohol dehydrogenase 5 (class III), chi polypeptide; ADIPOQ: adiponectin, C1Q and collagen domain containing; ATG: autophagy related; BECN1: beclin 1; CRTC2: CREB regulated transcription coactivator 2; ER: endoplasmic reticulum; F2RL1: F2R like trypsin receptor 1; FA: fatty acid; FOXO1: forkhead box O1; GLP1R: glucagon like peptide 1 receptor; GRK2: G protein-coupled receptor kinase 2; GTPase: guanosine triphosphatase; HFD: high-fat diet; HSCs: hepatic stellate cells; HTRA2: HtrA serine peptidase 2; IRGM: immunity related GTPase M; KD: knockdown; KDM6B: lysine demethylase 6B; KO: knockout; LAMP2: lysosomal associated membrane protein 2; LAP: LC3-associated phagocytosis; LDs: lipid droplets; Li KO: liver-specific knockout; LSECs: liver sinusoidal endothelial cells; MAP1LC3/LC3: microtubule associated protein 1 light chain 3; MAP3K5: mitogen-activated protein kinase kinase kinase 5; MED1: mediator complex subunit 1; MTOR: mechanistic target of rapamycin kinase; MTORC1: mechanistic target of rapamycin complex 1; NAFLD: non-alcoholic fatty liver disease; NASH: non-alcoholic steatohepatitis; NFE2L2: NFE2 like bZIP transcription factor 2; NOS3: nitric oxide synthase 3; NR1H3: nuclear receptor subfamily 1 group H member 3; OA: oleic acid; OE: overexpression; OSBPL8: oxysterol binding protein like 8; PA: palmitic acid; RUBCNL: rubicon like autophagy enhancer; PLIN2: perilipin 2; PLIN3: perilipin 3; PPARA: peroxisome proliferator activated receptor alpha; PRKAA2/AMPK: protein kinase AMP-activated catalytic subunit alpha 2; RAB: member RAS oncogene family; RPTOR: regulatory associated protein of MTOR complex 1; SCD: stearoyl-CoA desaturase; SIRT1: sirtuin 1; SIRT3: sirtuin 3; SNARE: soluble N-ethylmaleimide-sensitive factor attachment protein receptor; SQSTM1/p62: sequestosome 1; SREBF1: sterol regulatory element binding transcription factor 1;SREBF2: sterol regulatory element binding transcription factor 2; STING1: stimulator of interferon response cGAMP interactor 1; STX17: syntaxin 17; TAGs: triacylglycerols; TFEB: transcription factor EB; TP53/p53: tumor protein p53; ULK1: unc-51 like autophagy activating kinase 1; VMP1: vacuole membrane protein 1.


Assuntos
Autofagia , Hepatopatia Gordurosa não Alcoólica , Humanos , Autofagia/genética , Hepatopatia Gordurosa não Alcoólica/genética , Proteína Supressora de Tumor p53 , Dieta Hiperlipídica/efeitos adversos , Células Endoteliais , Alvo Mecanístico do Complexo 1 de Rapamicina , Fatores de Transcrição , GTP Fosfo-Hidrolases , Esteróis , Histona Desmetilases com o Domínio Jumonji , Proteínas de Membrana
13.
J Chem Theory Comput ; 19(24): 9009-9017, 2023 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-38090757

RESUMO

The Dirac-Coulomb-Breit (DCB) operator is widely recognized for its ability to accurately capture relativistic effects and spin-physics in molecular calculations. However, due to its high computational cost, there is a need to develop low-scaling approximations without compromising accuracy. To tackle this challenge, it becomes essential to gain a deeper understanding of the DCB operator's behavior. This work aims to explore local integral approximations, shedding light on the locality of the parts of the charge-current distribution due to the small component. In particular, we propose an atomic Breit approximation that leverages an analysis of the behavior observed in a series of gold chains. Through benchmark studies of metal complexes, we evaluated the accuracy and performance of the proposed atomic Breit approximation. This work provides a comprehensive understanding of the behavior of the charge-current distribution in terms of its contributions from its AO basis constituents, facilitating the development of low-scaling methods that strike a balance between computational efficiency and accuracy.

14.
J Chem Phys ; 159(22)2023 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-38063221

RESUMO

Separating the Coulomb potential into short-range and long-range components enables the use of different electron repulsion integral algorithms for each component. The short-range part can be efficiently computed using the analytical algorithm due to the locality in both the Gaussian-type orbital basis and the short-range Coulomb potentials. The integrals for the long-range Coulomb potential can be approximated with the density fitting method. A very small auxiliary basis is sufficient for the density fitting method to accurately approximate the long-range integrals. This feature significantly reduces the computational efforts associated with the N4 scaling in density fitting algorithms. For large molecules, the range separation and long-range density fitting method outperforms the conventional analytical integral evaluation scheme employed in Hartree-Fock calculations and provides more than twice the overall performance. In addition, this method offers a higher accuracy compared to conventional density fitting methods. The error in the Hartree-Fock energy can be easily reduced to 0.1 µEh per atom or smaller.

15.
Chem Sci ; 15(1): 379-388, 2023 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-38131096

RESUMO

Atomically dispersed metal catalysts with excellent activity and stability are highly desired in heterogeneous catalysis. Herein, we synthesized zeolite-encaged Pd-based pseudo-single atoms via a facile and energy-efficient ligand-protected direct H2 reduction method. Cs-corrected scanning transmission electron microscopy, extended X-ray absorption, and pair distribution function measurements reveal that the metal species are close to atomic-level dispersion and completely confined within the intersectional channels of silicalite-1 (S-1) zeolite with the MFI framework. The Pd@S-1-H exhibits excellent activity and stability in methane combustion reactions with a complete combustion temperature of 390 °C, and no deactivation is observed even after 100 h on stream. The optimized bimetallic 0.8Pd0.2Ni(OH)2@S-1-H catalyst exhibits an excellent H2 generation rate from FA decomposition without any additives, affording a superhigh turnover frequency up to 9308 h-1 at 333 K, which represents the top activity among all of the best heterogeneous catalysts under similar conditions. Significantly, zeolite-encaged metal catalysts are first used for Cr(vi) reduction coupled with formic acid (FA) dehydrogenation and show a superhigh turnover number of 2980 mol(Cr2O72-) mol(Pd)-1 at 323 K, surpassing all of the previously reported catalysts. This work demonstrates that zeolite-encaged pseudo-single atom catalysts are promising in efficient hydrogen storage and pollutant disposal applications.

16.
Nat Commun ; 14(1): 7476, 2023 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-37978295

RESUMO

As a major neuron type in the brain, the excitatory neuron (EN) regulates the lifespan in C. elegans. How the EN acquires senescence, however, is unknown. Here, we show that growth differentiation factor 11 (GDF11) is predominantly expressed in the EN in the adult mouse, marmoset and human brain. In mice, selective knock-out of GDF11 in the post-mitotic EN shapes the brain ageing-related transcriptional profile, induces EN senescence and hyperexcitability, prunes their dendrites, impedes their synaptic input, impairs object recognition memory and shortens the lifespan, establishing a functional link between GDF11, brain ageing and cognition. In vitro GDF11 deletion causes cellular senescence in Neuro-2a cells. Mechanistically, GDF11 deletion induces neuronal senescence via Smad2-induced transcription of the pro-senescence factor p21. This work indicates that endogenous GDF11 acts as a brake on EN senescence and brain ageing.


Assuntos
Caenorhabditis elegans , Fatores de Diferenciação de Crescimento , Adulto , Camundongos , Humanos , Animais , Caenorhabditis elegans/metabolismo , Fatores de Diferenciação de Crescimento/genética , Fatores de Diferenciação de Crescimento/metabolismo , Envelhecimento/genética , Encéfalo/metabolismo , Neurônios/metabolismo , Proteínas Morfogenéticas Ósseas
17.
Opt Express ; 31(21): 34542-34559, 2023 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-37859208

RESUMO

With the arrival of the 5th generation mobile network, the number of user devices is increasing exponentially, and thus it is necessary to expand the capacity of transmission systems. In order to further improve the system spectral efficiency on the basis of existing mobile fronthaul devices, we propose a hybrid digital-analog fronthaul transmission system with adaptive insertion of analog bandwidth, which can dynamically change the position of inserted analog bandwidth based on the state information of free space optical (FSO) channel. We consider the effects of atmospheric attenuation and turbulence on the FSO channel and derive an analytical expression for the maximum analog signal bandwidth that can be inserted into the first null of the digital signal spectrum to meet BER requirement of 3.8 × 10-3. Through a comprehensive simulation, it is verified that the analog bandwidth is obtained by this expression can exactly represent the lower bound of the simulation results under weak turbulence condition. The obtained results show that the maximum insertable analog bandwidth beyond the spectral null of the digital signal can reach 10% of the digital signal bandwidth, even in the FSO link with a transmission distance of 0.5 km and attenuation factor of 8 dB/km.

18.
Angew Chem Int Ed Engl ; 62(47): e202313174, 2023 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-37799095

RESUMO

Chemical upcycling that catalyzes waste plastics back to high-purity chemicals holds great promise in end-of-life plastics valorization. One of the main challenges in this process is the thermodynamic limitations imposed by the high intrinsic entropy of polymer chains, which makes their adsorption on catalysts unfavorable and the transition state unstable. Here, we overcome this challenge by inducing the catalytic reaction inside mesoporous channels, which possess a strong confined ability to polymer chains, allowing for stabilization of the transition state. This approach involves the synthesis of p-Ru/SBA catalysts, in which Ru nanoparticles are uniformly distributed within the channels of an SBA-15 support, using a precise impregnation method. The unique design of the p-Ru/SBA catalyst has demonstrated significant improvements in catalytic performance for the conversion of polyethylene into high-value liquid fuels, particularly diesel. The catalyst achieved a high solid conversion rate of 1106 g ⋅ gRu -1 ⋅ h-1 at 230 °C. Comparatively, this catalytic activity is 4.9 times higher than that of a control catalyst, Ru/SiO2 , and 14.0 times higher than that of a commercial catalyst, Ru/C, at 240 °C. This remarkable catalytic activity opens up immense opportunities for the chemical upcycling of waste plastics.

19.
Mol Cell ; 83(19): 3485-3501.e11, 2023 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-37802024

RESUMO

p62 is a well-characterized autophagy receptor that recognizes and sequesters specific cargoes into autophagosomes for degradation. p62 promotes the assembly and removal of ubiquitinated proteins by forming p62-liquid droplets. However, it remains unclear how autophagosomes efficiently sequester p62 droplets. Herein, we report that p62 undergoes reversible S-acylation in multiple human-, rat-, and mouse-derived cell lines, catalyzed by zinc-finger Asp-His-His-Cys S-acyltransferase 19 (ZDHHC19) and deacylated by acyl protein thioesterase 1 (APT1). S-acylation of p62 enhances the affinity of p62 for microtubule-associated protein 1 light chain 3 (LC3)-positive membranes and promotes autophagic membrane localization of p62 droplets, thereby leading to the production of small LC3-positive p62 droplets and efficient autophagic degradation of p62-cargo complexes. Specifically, increasing p62 acylation by upregulating ZDHHC19 or by genetic knockout of APT1 accelerates p62 degradation and p62-mediated autophagic clearance of ubiquitinated proteins. Thus, the protein S-acylation-deacylation cycle regulates p62 droplet recruitment to the autophagic membrane and selective autophagic flux, thereby contributing to the control of selective autophagic clearance of ubiquitinated proteins.


Assuntos
Autofagossomos , Proteínas Ubiquitinadas , Camundongos , Ratos , Humanos , Animais , Autofagossomos/metabolismo , Proteínas Ubiquitinadas/metabolismo , Proteína Sequestossoma-1/genética , Proteína Sequestossoma-1/metabolismo , Autofagia/genética , Acilação , Proteínas Associadas aos Microtúbulos/genética , Proteínas Associadas aos Microtúbulos/metabolismo , Mamíferos/metabolismo
20.
Environ Sci Technol ; 57(42): 16121-16130, 2023 10 24.
Artigo em Inglês | MEDLINE | ID: mdl-37842921

RESUMO

Ammonia-mediated selective catalytic reduction (NH3-SCR) is currently the key approach to abate nitrogen oxides (NOx) emitted from heavy-duty lean-burn vehicles. The state-of-art NH3-SCR catalysts, namely, copper ion-exchanged chabazite (Cu-CHA) zeolites, perform rather poorly at low temperatures (below 200 °C) and are thus incapable of eliminating effectively NOx emissions under cold-start conditions. Here, we demonstrate a significant promotion of low-temperature NOx reduction by reinforcing the dynamic motion of zeolite-confined Cu sites during NH3-SCR. Combining complex impedance-based in situ spectroscopy (IS) and extended density-functional tight-binding molecular dynamics simulation, we revealed an environment- and temperature-dependent nature of the dynamic Cu motion within the zeolite lattice. Further coupling in situ IS with infrared spectroscopy allows us to unravel the critical role of monovalent Cu in the overall Cu mobility at a molecular level. Based on these mechanistic understandings, we elicit a boost of NOx reduction below 200 °C by reinforcing the dynamic Cu motion in various Cu-zeolites (Cu-CHA, Cu-ZSM-5, Cu-Beta, etc.) via facile postsynthesis treatments, either in a reductive mixture at low temperatures (below 250 °C) or in a nonoxidative atmosphere at high temperatures (above 450 °C).


Assuntos
Zeolitas , Zeolitas/química , Cobre , Amônia/química , Óxidos de Nitrogênio/química , Temperatura , Catálise
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