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1.
Int J Biol Macromol ; : 132234, 2024 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-38763239

RESUMO

Lignin, a renewable natural antioxidant and bacteriostat, holds promise as a versatile, cost-effective feed additive. However, traditional industrial lignin faces limitations, including low reactivity, poor uniformity, and unstable properties, necessitating chemical modification. Complex modification methods pose economic and toxicity challenges, so this study adopted a relatively simple alkali-catalyzed phenolization approach, using phenol, catechol, and pyrogallol to modify kraft lignin, and characterized the resulting products using various techniques. Subsequently, their antioxidant, antibacterial, adsorption properties for heavy metal ions and mycotoxins, growth-promoting properties, and antiviral abilities were assessed. The phenolation process led to lignin depolymerization and a notable increase in phenolic hydroxyl content, particularly in pyrogallol-phenolated lignin (Py-L), rising from 3.08 to 4.68 mmol/g. These modified lignins exhibited enhanced antioxidant activity, with over 99 % inhibition against E. coli and S. aureus, and remarkable adsorption capacities for heavy metal ions and mycotoxins. Importantly, Py-L improved the growth performance of mice and reduced influenza mortality. Furthermore, density functional theory calculations elucidated the mechanism behind the enhanced antioxidant properties. This study presents a promising avenue for developing versatile feed additives to address challenges related to animal feed antioxidant supplementation, bacterial control, and growth promotion.

2.
J Chem Theory Comput ; 20(9): 3426-3439, 2024 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-38656202

RESUMO

Herein, we have used the "on-the-fly" ring-polymer surface-hopping simulation method with the centroid approximation (RPSH-CA), in combination with the multireference OM2/MRCI electronic structure calculations to study the photoinduced dynamics of a green fluorescent protein (GFP) chromophore analogue in the gas phase, i.e., o-HBI, at 50, 100, and 300 K with 1, 5, 10, and 15 beads (3600 1 ps trajectories). The electronic structure calculations identified five new minimum-energy conical intersection (MECI) structures, which, together with the previous one, play crucial roles in the excited-state decay dynamics of o-HBI. It is also found that the excited-state intramolecular proton transfer (ESIPT) occurs in an ultrafast manner and is completed within 20 fs in all the simulation conditions because there is no barrier associated with this ESIPT process in the S1 state. However, the other excited-state dynamical results are strongly related to the number of beads. At 50 and 100 K, the nuclear quantum effects (NQEs) are very important; therefore, the excited-state dynamical results change significantly with the bead number. For example, the S1 decay time deduced from time-dependent state populations becomes longer as the bead number increases. Nevertheless, an essentially convergent trend is observed when the bead number is close to 10. In contrast, at 300 K, the NQEs become weaker and the above dynamical results converge very quickly even with 1 bead. Most importantly, the NQEs seriously affect the excited-state decay mechanism of o-HBI. At 50 and 100 K, most trajectories decay to the S0 state via perpendicular keto MECIs, whereas, at 300 K, only twisted keto MECIs are responsible for the excited-state decay. The present work not only comprehensively explores the temperature-dependent photoinduced dynamics of o-HBI, but also demonstrates the importance and necessity of NQEs in nonadiabatic dynamics simulations, especially at relatively low temperatures.

3.
Nano Lett ; 24(15): 4691-4701, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38588212

RESUMO

Tumor cells exhibit heightened glucose (Glu) consumption and increased lactic acid (LA) production, resulting in the formation of an immunosuppressive tumor microenvironment (TME) that facilitates malignant proliferation and metastasis. In this study, we meticulously engineer an antitumor nanoplatform, denoted as ZLGCR, by incorporating glucose oxidase, LA oxidase, and CpG oligodeoxynucleotide into zeolitic imidazolate framework-8 that is camouflaged with a red blood cell membrane. Significantly, ZLGCR-mediated consumption of Glu and LA not only amplifies the effectiveness of metabolic therapy but also reverses the immunosuppressive TME, thereby enhancing the therapeutic outcomes of CpG-mediated antitumor immunotherapy. It is particularly important that the synergistic effect of metabolic therapy and immunotherapy is further augmented when combined with immune checkpoint blockade therapy. Consequently, this engineered antitumor nanoplatform will achieve a cooperative tumor-suppressive outcome through the modulation of metabolism and immune responses within the TME.


Assuntos
Neoplasias , Microambiente Tumoral , Humanos , Imunoterapia , Radioimunoterapia , Glucose , Glucose Oxidase , Imunossupressores , Ácido Láctico , Neoplasias/terapia , Linhagem Celular Tumoral
4.
Free Radic Biol Med ; 218: 26-40, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38570172

RESUMO

Nuclear factor erythroid 2-related factor 2 (Nrf2) plays a crucial role in ferroptosis by regulating the cellular antioxidant response and maintaining redox balance. However, compounds that induce ferroptosis through dual antioxidant pathways based on Nrf2 have not been fully explored. In our study, we investigated the impact of Gambogic acid (GA) on MCF-7 cells and HepG2 cells in vitro. The cytotoxicity, colony formation assay and cell cycle assay demonstrated potent tumor-killing ability of GA, while its effect was rescued by ferroptosis inhibitors. Furthermore, RNA sequencing revealed the enrichment of ferroptosis pathway mediated by GA. In terms of ferroptosis indicators detection, evidences for GA were provided including reactive oxygen species (ROS) accumulation, alteration in mitochondrial membrane potential (MMP), disappearance of mitochondrial cristae, lipid peroxidation induction, malondialdehyde (MDA) accumulation promotion, iron ion accumulation as well as glutathione (GSH)/thioredoxin (Trx) depletion. Notably, Ferrostatin-1 (Fer-1) and Liproxstatin-1 (Lip-1) successfully rescued GA-induced MDA accumulation. In terms of mechanism, Nrf2 was found to play a pivotal role in GA-induced ferroptosis by inducing protein alterations through the iron metabolism pathway and GSH/Trx dual antioxidant pathway. Furthermore, GA exerted good antitumor activity in vivo through GSH/Trx dual antioxidant pathway, and Fer-1 significantly attenuated its efficacy. In conclusion, our findings first provided new evidence for GA as an inducer of ferroptosis, and Nrf2-mediated GSH/Trx dual antioxidant system played an important role in GA-induced ferroptosis.


Assuntos
Antioxidantes , Ferroptose , Glutationa , Fator 2 Relacionado a NF-E2 , Quinoxalinas , Espécies Reativas de Oxigênio , Compostos de Espiro , Xantonas , Ferroptose/efeitos dos fármacos , Xantonas/farmacologia , Humanos , Fator 2 Relacionado a NF-E2/metabolismo , Fator 2 Relacionado a NF-E2/genética , Glutationa/metabolismo , Animais , Antioxidantes/farmacologia , Espécies Reativas de Oxigênio/metabolismo , Camundongos , Células MCF-7 , Células Hep G2 , Ensaios Antitumorais Modelo de Xenoenxerto , Potencial da Membrana Mitocondrial/efeitos dos fármacos , Antineoplásicos/farmacologia , Peroxidação de Lipídeos/efeitos dos fármacos , Cicloexilaminas/farmacologia , Fenilenodiaminas/farmacologia , Proliferação de Células/efeitos dos fármacos
5.
J Phys Chem A ; 128(17): 3311-3320, 2024 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-38654690

RESUMO

Herein, we employed linear-response time-dependent functional theory nonadiabatic dynamic simulations to explore the photoinduced exciton dynamics of a chiral single-walled carbon nanotube CNT(6,5) covalently doped with a 4-nitrobenzyl group (CNT65-NO2). The results indicate that the introduction of a sp3 defect leads to the splitting of the degenerate VBM/VBM-1 and CBM/CBM+1 states. Both the VBM upshift and the CBM downshift are responsible for the experimentally observed redshifted E11* trapping state. The simulations reveal that the photoinduced exciton relaxation dynamics completes within 500 fs, which is consistent with the experimental work. On the other hand, we also conducted the nonadiabatic carrier (electron and hole) dynamic simulations, which completely ignore the excitonic effects. The comparison demonstrates that excitonic effects are indispensable. Deep analyses show that such effects induce several dark states, which play an important role in regulating the photoinduced dynamics of CNT65-NO2. The present work demonstrates the importance of including excitonic effects in simulating photoinduced processes of carbon nanotubes. In addition, it not only rationalizes previous experiments but also provides valuable insights that will help in the future rational design of novel covalently doped carbon nanotubes with superior photoluminescent properties.

6.
Proc Natl Acad Sci U S A ; 121(15): e2315730121, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38557188

RESUMO

Microdroplets are a class of soft matter that has been extensively employed for chemical, biochemical, and industrial applications. However, fabricating microdroplets with largely controllable contact-area shape and apparent contact angle, a key prerequisite for their applications, is still a challenge. Here, by engineering a type of surface with homocentric closed-loop microwalls/microchannels, we can achieve facile size, shape, and contact-angle tunability of microdroplets on the textured surfaces by design. More importantly, this class of surface topologies (with universal genus value = 1) allows us to reveal that the conventional Gibbs equation (widely used for assessing the edge effect on the apparent contact angle of macrodroplets) seems no longer applicable for water microdroplets or nanodroplets (evidenced by independent molecular dynamics simulations). Notably, for the flat surface with the intrinsic contact angle ~0°, we find that the critical contact angle on the microtextured counterparts (at edge angle 90°) can be as large as >130°, rather than 90° according to the Gibbs equation. Experiments show that the breakdown of the Gibbs equation occurs for microdroplets of different types of liquids including alcohol and hydrocarbon oils. Overall, the microtextured surface design and topological wetting states not only offer opportunities for diverse applications of microdroplets such as controllable chemical reactions and low-cost circuit fabrications but also provide testbeds for advancing the fundamental surface science of wetting beyond the Gibbs equation.

7.
Front Psychol ; 15: 1293857, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38605848

RESUMO

Introduction: Despite the rapid growth of interdisciplinary resilience research in Chinese contexts, no study has systematically reviewed individual-level measurement scales for Chinese-speaking populations. We report a systematic review of scales developed for or translated/adapted to Chinese-speaking contexts, where we assessed how widely used scales fare in terms of their psychometric qualities. Methods: Studies included in this review must have been published in peer-reviewed English or Chinese journals between 2015-2020 and included self-reported resilience scales in Chinese-speaking populations. Searches were conducted in PsycINFO, CNKI (completed in May 2021), and PubMed (completed in January 2024). We developed coding schemes for extracting relevant data and adapted and applied an existing evaluation framework to assess the most frequently used resilience scales by seven methodological criteria. Results: Analyses of 963 qualified studies suggested that Chinese resilience scales were used in a diverse range of study contexts. Among 85 unique kinds of resilience measures, we highlighted and evaluated the three most frequently used translated scales and three locally developed scales (nine scales in total including variations such as short forms). In short, resilience studies in Chinese contexts relied heavily on the translated 25-item Connor-Davidson Resilience Scale, which scored moderately on the overall quality. The locally developed Resilience Scale for Chinese Adolescents and Essential Resilience Scale received the best ratings but could use further development. Discussion: We discussed how future work may advance widely used scales, and specified seven methodological recommendations for future resilience scale development with existing and new scales in and beyond the Chinese study contexts. We further addressed issues and challenges in measuring resilience as a process and called on researchers to further develop/evaluate process measures for Chinese-speaking populations.

8.
Clin Interv Aging ; 19: 613-626, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38646591

RESUMO

Purpose: This study aims to investigate how the type of anesthesia used during major orthopedic surgery may impact adverse short-term postoperative outcomes depending on frailty. Methods: To conduct this investigation, we recruited individuals aged 65 years and older who underwent major orthopedic surgery between March 2022 and April 2023 at a single institution. We utilized the FRAIL scale to evaluate frailty. The primary focus was on occurrences of death or the inability to walk 60 days after the surgery. Secondary measures included death within 60 days; inability to walk without human assistance at 60 days; death or the inability to walk without human assistance at 30 days after surgery, the first time out of bed after surgery, postoperative blood transfusion, length of hospital stay, hospital costs, and the occurrence of surgical complications such as dislocation, periprosthetic fracture, infection, reoperation, wound complications/hematoma. Results: In a study of 387 old adult patients who had undergone major orthopedic surgery, 41.3% were found to be in a frail state. Among these patients, 262 had general anesthesia and 125 had neuraxial anesthesia. Multifactorial logistic regression analyses showed that anesthesia type was not linked to complications. Instead, frailty (OR 4.04, 95% CI 1.04 to 8.57, P< 0.001), age (OR 1.05, 95% CI 1.00-1.10, P= 0.017), and aCCI scores, age-adjusted Charlson Comorbidity Index, (OR 1.36, 95% CI 1.12 to 1.66, P= 0.002) were identified as independent risk factors for death or new walking disorders in these patients 60 days after surgery. After adjusting for frailty, anesthesia methods was not associated with the development of death or new walking disorders in these patients (P > 0.05). Conclusion: In different frail populations, neuraxial anesthesia is likely to be comparable to general anesthesia in terms of the incidence of short-term postoperative adverse outcomes.


Assuntos
Fragilidade , Tempo de Internação , Procedimentos Ortopédicos , Complicações Pós-Operatórias , Idoso , Idoso de 80 Anos ou mais , Feminino , Humanos , Masculino , Anestesia Geral/efeitos adversos , Idoso Fragilizado , Tempo de Internação/estatística & dados numéricos , Modelos Logísticos , Procedimentos Ortopédicos/efeitos adversos , Complicações Pós-Operatórias/epidemiologia , Estudos Prospectivos , Fatores de Risco
9.
Adv Sci (Weinh) ; 11(17): e2310262, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38425136

RESUMO

Ensuring information security has emerged as a paramount concern in contemporary human society. Substantial advancements in this regard can be achieved by leveraging photonic signals as the primary information carriers, utilizing photonic logical gates capable of wavelength tunability across various time and spatial domains. However, the challenge remains in the rational design of materials possessing space-time-color multiple-resolution capabilities. In this work, a facile approach is proposed for crafting metal-organic halides (MOHs) that offer space-time-color resolution. These MOHs integrate time-resolved room temperature phosphorescence and color-resolved excitation wavelength dependencies with both space-resolved ex situ optical waveguides and in situ heterojunctions. Capitalizing on these multifaceted properties, MOHs-based two-dimensional (2D) optical waveguides and heterojunctions exhibit the ability to tune full-color emissions across the spectra from blue to red, operating within different spatial and temporal scales. Therefore, this work introduces an effective methodology for engineering space-time-color resolved MOH microstructures, holding significant promise for the development of high-density photonic logical devices.

10.
Angew Chem Int Ed Engl ; 63(21): e202402634, 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38466630

RESUMO

Molecular ultralong room-temperature phosphorescence (RTP), exhibiting multiple stimuli-responsive characteristics, has garnered considerable attention due to its potential applications in light-emitting devices, sensors, and information safety. This work proposes the utilization of photochemical cascade processes (PCCPs) in molecular crystals to design a stepwise smart RTP switch. By harnessing the sequential dynamics of photo-burst movement (induced by [2+2] photocycloaddition) and photochromism (induced by photogenerated radicals) in a bismuth (Bi)-based metal-organic halide (MOH), a continuous and photo-responsive ultralong RTP can be achieved. Furthermore, utilizing the same Bi-based MOH, diverse application demonstrations, such as multi-mode anti-counterfeiting and information encryption, can be easily implemented. This work thus not only serves as a proof-of-concept for the development of solid-state PCCPs that integrate photosalient effect and photochromism with light-chemical-mechanical energy conversion, but also lays the groundwork for designing new Bi-based MOHs with dynamically responsive ultralong RTP.

11.
J Phys Chem Lett ; 15(14): 3764-3771, 2024 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-38552186

RESUMO

In this study, we developed a machine-learned force field for CsPbI3 using a neural network potential, enabling molecular dynamics simulations (MD) with ab initio accuracy over nanoseconds. This approach, combined with ab initio MD and nonadiabatic MD, was used to study the charge trapping and recombination dynamics in both pristine and defective CsPbI3. Our simulations revealed key transitions affecting carrier lifetimes, especially in systems with iodine vacancy and interstitial iodine defects. An iodine trimer, formed when iodine replaces cesium, exhibits a high-frequency phonon mode. This mode enhances nonadiabatic coupling, accelerating charge recombination in defective systems compared to pristine ones. In the iodine vacancy system, recombination times varied significantly due to differences in NA coupling and energy gaps. The interplay between nonadiabatic coupling and pure dephasing time is crucial in determining recombination times for interstitial iodine defects. Our findings highlight the role of defect evolution in perovskites, offering insights for enhancing perovskite performance.

12.
Nat Commun ; 15(1): 2347, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38491022

RESUMO

Reactive uptake of dinitrogen pentaoxide (N2O5) into aqueous aerosols is a major loss channel for NOx in the troposphere; however, a quantitative understanding of the uptake mechanism is lacking. Herein, a computational chemistry strategy is developed employing high-level quantum chemical methods; the method offers detailed molecular insight into the hydrolysis and ammonolysis mechanisms of N2O5 in microdroplets. Specifically, our calculations estimate the bulk and interfacial hydrolysis rates to be (2.3 ± 1.6) × 10-3 and (6.3 ± 4.2) × 10-7 ns-1, respectively, and ammonolysis competes with hydrolysis at NH3 concentrations above 1.9 × 10-4 mol L-1. The slow interfacial hydrolysis rate suggests that interfacial processes have negligible effect on the hydrolysis of N2O5 in liquid water. In contrast, N2O5 ammonolysis in liquid water is dominated by interfacial processes due to the high interfacial ammonolysis rate. Our findings and strategy are applicable to high-chemical complexity microdroplets.

13.
JACS Au ; 4(2): 419-431, 2024 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-38425917

RESUMO

The synthesis of 1-aminonorbornane (1-aminoNB), a potential aniline bioisostere, through photochemistry or photoredox catalysis signifies a remarkable breakthrough with implications in organic chemistry, pharmaceutical chemistry, and sustainable chemistry. However, an understanding of the underlying mechanisms involved in these reactions remains limited and ambiguous. Herein, we employ high-precision CASPT2//CASSCF calculations to elucidate the intricate mechanisms regulating the intramolecular photo-(3 + 2)-cycloaddition reactions for the synthesis of 1-aminoNB in the presence or absence of the Ir-complex-based photocatalyst. Our investigations delve into radical cascades, stereoselectivity, particularly single-electron-transfer (SET) events, etc. Furthermore, we innovatively introduce and compare two SET models integrating Marcus electron-transfer theory and transition-state theory. These models combined with kinetic data contribute to recognizing the critical control factors in diverse photocatalysis, thereby guiding the design and manipulation of photoredox catalysis as well as the improvement and modification of photocatalysts.

14.
JACS Au ; 4(2): 441-453, 2024 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-38425924

RESUMO

A small chemical modification of the nucleobase structure can significantly enhance the photoactivity of DNA, which may incur DNA damage, thus holding promising applications in photochemotherapy treatment of cancers or pathogens. However, single substitution confers only limited phototoxicity to DNA. Herein, we combine femtosecond and nanosecond time-resolved spectroscopy with high-level ab initio calculations to disentangle the excited-state dynamics of 6-methylthioguanine (me6-TG) under variable wavelength UVA excitation (310-330 nm). We find that double substitution of nucleobases (thionation and methylation) boosts the photoactivity by introducing more reactive channels. Intriguingly, 1nNπ*, rather than 1nSπ*, acts as the doorway state engendering the formation of the long-lived reactive triplet state in me6-TG. The 1nNπ* induces a low spin-orbit coupling of 8.3 cm-1, which increases the intersystem crossing (ISC) time (2.91 ± 0.14 ns). Despite the slowed ISC, the triplet quantum yield (ΦT) still accounts for a large fraction (0.6 ± 0.1), consistent with the potential energy surface that favors excited-state bifurcation to 1nNπ*min (3.36 ± 0.15 ps) rather than 1ππ*min (5.05 ± 0.26 ps), such that the subsequent ISC to triplet via 1nNπ*min constitutes the main relaxation pathway in me6-TG. Although this ΦT is inferior to its single-substituted predecessor 6-thioguanine (6-TG, 0.8 ± 0.2), the effect of thionation in synergy with methylation opens a unique C-S bond cleavage pathway through crossing to a repulsive 1πσ* state, generating thiyl radicals as highly reactive intermediates that may invoke biological damage. This photodissociation channel is extremely difficult for conventional nucleobases. These findings demonstrate the synergistic effects of double functionality substitution in modulating excited-state dynamics and enhancing the photolabile character of DNA nucleobases, providing inspirations for the rational design of advanced photodynamic and photochemotherapy approaches.

16.
Artigo em Inglês | MEDLINE | ID: mdl-38536209

RESUMO

Three bacterial strains, FP250T, FP821, and FP53, were isolated from the rhizosphere soil of oilseed rape, licorice, and habanero pepper in Anhui Province, Xinjiang Uygur Autonomous Region, and Jiangsu Province, PR China, respectively. All strains were shown to grow at 4-37 °C and pH 6.0-9.0, and in the presence of 0-4.0 % (w/v) NaCl. Phylogenetic analyses based on 16S rRNA gene sequences or housekeeping genes (16S rRNA, gyrB, rpoB, and rpoD) and phylogenomic analysis showed that strains FP250T, FP821, and FP53 belong to the genus Pseudomonas, and are closely related to Pseudomonas kilonensis DSM 13647T, Pseudomonas brassicacearum JCM 11938T, Pseudomonas viciae 11K1T, and Pseudomonas thivervalensis DSM 13194T. The DNA G+C content of strain FP205T was 59.8 mol%. The average nucleotide identity and digital DNA-DNA hybridization values of strain FP205T with the most closely related strain were 93.2 % and 51.4 %, respectively, which is well below the threshold for species differentiation. Strain FP205T contained summed feature 3 (C16 : 1 ω6c and/or C16 : 1 ω7c), summed feature 8 (C18 : 1 ω7c and/or C18 : 1 ω6c) as major fatty acids, and diphosphatidylglycerol along with phosphatidylethanolamine and aminophospholipid as major polar lipids. The predominant isoprenoid quinone was ubiquinone-9. Based on these phenotypic, phylogenetic, and chemotaxonomic results, strain FP205T represents a novel species of the genus Pseudomonas, for which the name Pseudomonas hefeiensis sp. nov. is proposed. The type strain is FP205T (=ACCC 62447T=JCM 35687T).


Assuntos
Ácidos Graxos , Rizosfera , Composição de Bases , Ácidos Graxos/química , Filogenia , RNA Ribossômico 16S/genética , Análise de Sequência de DNA , DNA Bacteriano/genética , Técnicas de Tipagem Bacteriana , China
17.
J Chem Theory Comput ; 20(5): 1912-1922, 2024 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-38354395

RESUMO

Variational wave function ansätze are at the heart of solving quantum many-body problems in physics and chemistry. Previous designs of hardware-efficient ansatz (HEA) on quantum computers are largely based on heuristics and lack rigorous theoretical foundations. In this work, we introduce a physics-constrained approach for designing HEA with rigorous theoretical guarantees by imposing a few fundamental constraints. Specifically, we require that the target HEA to be universal, systematically improvable, and size-consistent, which is an important concept in quantum many-body theories for scalability but has been overlooked in previous designs of HEA. We extend the notion of size-consistency to HEA and present a concrete realization of HEA that satisfies all these fundamental constraints while only requiring linear qubit connectivity. The developed physics-constrained HEA is superior to other heuristically designed HEA in terms of both accuracy and scalability, as demonstrated numerically for the Heisenberg model and some typical molecules. In particular, we find that restoring size-consistency can significantly reduce the number of layers needed to reach a certain accuracy. In contrast, the failure of other HEA to satisfy these constraints severely limits their scalability to larger systems with more than 10 qubits. Our work highlights the importance of incorporating physical constraints into the design of HEA for efficiently solving many-body problems on quantum computers.

18.
J Phys Chem A ; 128(3): 528-538, 2024 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-38215031

RESUMO

The arylazopyrazole 3pzH as a novel photoswitch exhibits quantitative switching and high thermal stability. In this work, combined electronic structure calculations and ab initio multiple spawning (AIMS) dynamic simulations were performed to systemically investigate the cis ↔ trans photoisomerization mechanism and the chiral preference after photoexcitation of 3pzH to the first excited singlet state (S1). Unlike most of the azoheteroarene photoswitches reported previously, many twisted and T-shaped cis isomers were found to be stable for 3pzH in the S0 state, owing to the moderate interaction between the hydrogen atom and π electrons of the aromatic ring. Two twisted cis isomers with different chirality ((M)-Z1 and (P)-Z1), the most stable T-shaped cis isomer ((T)-Z2), and the most stable planar trans isomer (E2) were selected as the initial structures to carry out the AIMS nonadiabatic dynamic simulations. Following excitation to the S1 state, all of the cis isomers decayed to conical intersection (CI) regions via the same bicycle pedal mechanism, while the evolution of the trans isomers to their CI regions was achieved via rotation around the N═N bond. More importantly, chiral preferences were found for the twisted cis isomers in the S1 state through the AIMS dynamic simulations due to the steric effect and static electronic repulsion. Notably, chirality was also observed in S1 isomerization starting from the planar E2 isomer because of the dynamic effect. After the nonadiabatic transition to the S0 state, the bicycle pedal mechanism was found to play a crucial role in cis ↔ trans photoisomerization. The simulated photoisomerization productivities were generally consistent with past experimental observations. Our calculations not only uncover the underlying reason for the excellent photoswitching properties of 3pzH but also enrich the knowledge of photoisomerization for azoheteroarene photoswitches, which will surely benefit their rational design.

19.
mSphere ; 9(2): e0066523, 2024 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-38231250

RESUMO

This study investigated the change in the microbiome of tomato rhizosphere soils after the invasion of Ralstonia solanacearum and analyzed the correlation between microbes and soil physicochemical properties. Diversity analyses of the bacteria in healthy and diseased rhizosphere soil samples (HRS and DRS) revealed that HRS had a higher species diversity and were compositionally different from DRS (P ≤ 0.05). Substantial differences in the relative abundance of Actinobacteria (37.52% vs 28.96%, P ≤ 0.05) and Proteobacteria (29.20% vs 35.59%, P ≤ 0.05) were identified in HRS and DRS, respectively. Taxonomic composition analysis showed ten differentially abundant genera, and seven of them (Gaiella, Roseisolibacter, Solirubrobacter, Kribbella, Acidibacter, Actinomarinicola, and Marmoricola) are more abundant in HRS. Soil pH and enzyme activities were negatively correlated with the abundance of R. solanacearum. The contents of total nitrogen (TN), total phosphorus (TP), total potassium (TK), alkaline nitrogen (alkaline N), available phosphorus (AP), available potassium (AK), NO3-N(NN), NH4+-N (AN), and organic matter (OM) were all significantly increased in DRS. The composition and richness of protozoa in the samples show significant differences. Cephalobus, Acrobeles, Heteromita, norank_Tylenchida, and Rotylenchulus were enriched in DRS. Microbial interaction networks revealed that the HRS networks were more complex than the DRS networks. Overall, the results of this study demonstrate that healthy soil has a more complex microbial community structure and higher enzyme activity, and the invasion of R. solanacearum damages the soil microbial system.IMPORTANCEHow does the invasion of Ralstonia solanacearum affect tomato rhizosphere bacteria and protozoa? Which microbial changes can affect the growth of R. solanacearum? To date, most research studies focus on bacteria, with little research on protozoa, and even less on the synergistic effects between protozoa and bacteria. Here, we analyzed the correlation between tomato rhizosphere bacterial and protozoan communities and soil physicochemical properties during the invasion of R. solanacearum. We found that the diversity and abundance of rhizosphere microorganisms in healthy rhizosphere soil samples (HRS) were significantly higher than those in diseased rhizosphere soil samples (DRS), and there were significant changes in soil pH and enzyme activity. Overall, in this study, the analysis of microbial changes during the invasion of R. solanacearum provides a theoretical basis for the prevention and control of bacterial wilt.


Assuntos
Microbiota , Ralstonia solanacearum , Solanum lycopersicum , Solo/química , Microbiologia do Solo , Bactérias , China , Nitrogênio , Fósforo , Potássio
20.
Int J Stroke ; : 17474930241228203, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38229443

RESUMO

BACKGROUND: High-resolution magnetic resonance vessel wall imaging (HRMR-VWI) is a promising technique for identifying intracranial vulnerable plaques beyond lumen narrowing. However, the association between HRMR-VWI characteristics and recurrent stroke remains uncertain. AIMS: This study aimed to investigate the association between HRMR-VWI characteristics and recurrent ipsilateral stroke in patients with symptomatic intracranial atherosclerotic steno-occlusive disease (ICAS). METHODS: This multicenter, observational study recruited first-ever acute ischemic stroke patients attributed to ICAS (>50% stenosis or occlusion) within 7 days after onset. Participants were assessed by multiparametric magnetic resonance imaging (MRI) including diffusion-weighted imaging, three-dimension time-of-flight magnetic resonance angiography, and three-dimensional T1-weighted HRMR-VWI. The patients were recommended to receive best medical therapy and were systematically followed up for 12 months. The association between HRMR-VWI characteristics and the time to recurrent ipsilateral stroke was investigated by univariable and multivariable analysis. RESULTS: Two hundred and fifty-five consecutive patients were enrolled from 15 centers. The cumulative 12 month ipsilateral recurrence incidence was 4.1% (95% confidence interval (CI): 1.6-6.6%). Patients with recurrent ipsilateral stroke exhibited higher rates of intraplaque hemorrhage (IPH) (30.0% vs 6.5%) and eccentric plaque (90.0% vs 48.2%), and lower occurrence of occlusive thrombus (10.0% vs 23.7%). Plaque length (5.69 ± 2.21 mm vs 6.67 ± 4.16 mm), plaque burden (78.40 ± 7.37% vs 78.22 ± 8.32%), degree of stenosis (60.25 ± 18.95% vs 67.50% ± 22.09%) and remodeling index (1.07 ± 0.27 vs 1.03 ± 0.35) on HRMR-VWI did not differ between patients with and without recurrent ipsilateral stroke. In the multivariable Cox regression analysis, IPH (hazard ratio: 6.64, 95% CI: 1.23-35.8, p = 0.028) was significantly associated with recurrent ipsilateral stroke after adjustment.Conclusions:Our results suggest intraplaque hemorrhage (IPH) is significantly associated with recurrent ipsilateral stroke and has potential value in the selection of patients for aggressive treatment strategies. DATA ACCESS STATEMENT: Data from this study are available and can be accessed upon request.

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