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1.
Angew Chem Int Ed Engl ; : e202408769, 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38960984

RESUMO

The clinical application of photodynamic therapy (PDT) is limited by oxygen-dependence and side effects caused by photosensitizer residues. Photoinitiators based on the H-abstraction reaction can address these challenges because they can generate alkyl radical-killing cells independently of oxygen and undergo rapid bleaching following H-abstraction. Nonetheless, the development of photoinitiators for PDT has been impeded by the absence of effective design strategies. Herein, we have developed aryl-ketone substituted cyanine (ACy-R), the first red-light triggered H-abstraction photoinitiators for hypoxic cancer therapy. These ACy-R molecules inherited the near-infrared absorption of cyanine dye, and aryl-ketone modification imparted H-abstraction capability. Experimental and quantum calculations revealed that modifying the electron-withdrawing groups of the aryl (e.g., ACy-5F) improved the contribution of the O atom to the photon excitation process promoting intersystem crossing and H-abstraction ability. Particularly, ACy-5F rapidly penetrated cells and enriched in the endoplasmic reticulum. Even under severe hypoxia, ACy-5F initiated red-light induced H-abstraction with intracellular biomolecules, inducing necroptosis and ferroptosis. Moreover, ACy-5F was degraded after H-abstraction, thus avoiding the side effects of long-term phototoxicity after therapy. This study not only provides a crucial molecular tool for hypoxic tumors therapy, but also presents a promising strategy for the development of multifunctional photosensitizers and photoinitiators.

2.
Nat Mater ; 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38951651

RESUMO

Solution-processed colloidal nanocrystals of lead halide perovskites have been intensively investigated in recent years in the context of optoelectronic devices, during which time their quantum properties have also begun to attract attention. Their unmatched ease of synthetic tunability and unique structural, optical and electronic properties, in conjunction with the confinement of carriers in three dimensions, have motivated studies on observing and controlling coherent light-matter interaction in these materials for quantum information technologies. This Review outlines the recent efforts and achievements in this direction. Particularly notable examples are the observation of coherent single-photon emission, evidence for superfluorescence and the realization of room-temperature coherent spin manipulation for ensemble samples, which have not been achieved for prototypical colloidal CdSe nanocrystals that have been under investigation for decades. This Review aims to highlight these results, point out the challenges ahead towards realistic applications and bring together the efforts of multidisciplinary communities in this nascent field.

3.
Nat Commun ; 15(1): 5647, 2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-38969653

RESUMO

Direct reduction of unactivated alkyl halides for C(sp3)-N couplings under mild conditions presents a significant challenge in organic synthesis due to their low reduction potential. Herein, we introduce an in situ formed pyridyl-carbene-ligated copper (I) catalyst that is capable of abstracting halide atom and generating alkyl radicals for general C(sp3)-N couplings under visible light. Control experiments confirmed that the mono-pyridyl-carbene-ligated copper complex is the active species responsible for catalysis. Mechanistic investigations using transient absorption spectroscopy across multiple decades of timescales revealed ultrafast intersystem crossing (260 ps) of the photoexcited copper (I) complexes into their long-lived triplet excited states (>2 µs). The non-Stern-Volmer quenching dynamics of the triplets by unactivated alkyl halides suggests an association between copper (I) complexes and alkyl halides, thereby facilitating the abstraction of halide atoms via inner-sphere single electron transfer (SET), rather than outer-sphere SET, for the formation of alkyl radicals for subsequent cross couplings.

4.
J Am Chem Soc ; 146(28): 19360-19368, 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-39015060

RESUMO

High-efficiency generation of spin-triplet states in organic molecules is of great interest in diverse areas such as photocatalysis, photodynamic therapy, and upconversion photonics. Recent studies have introduced colloidal semiconductor nanocrystals as a new class of photosensitizers that can efficiently transfer their photoexcitation energy to molecular triplets. Here, we demonstrate that metallic Ag nanoparticles can also assist in the generation of molecular triplets in polycyclic aromatic hydrocarbons (PAHs), but not through a conventional sensitization mechanism. Instead, the triplet formation is mediated by charge-separated states resulting from hole transfer from photoexcited PAHs (anthracene and pyrene) to Ag nanoparticles, which is established through the rapid formation and subsequent decay of molecular anions revealed in our transient absorption measurements. The dominance of hole transfer over electron transfer, while both are energetically allowed, could be attributed to a Marcus inverted region of charge transfer. Owing to the rapid charge separation and the rapid spin-flip in metals, the triplet formation yields are remarkably high, as confirmed by their engagement in production of singlet oxygen with a quantum efficiency reaching 58.5%. This study not only uncovers the fundamental interaction mechanisms between metallic nanoparticles and organic molecules in both charge and spin degrees of freedom but also greatly expands the scope of triplet "sensitization" using inorganic nanomaterials for a variety of emerging applications.

5.
Front Cell Infect Microbiol ; 14: 1375312, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38779562

RESUMO

Competence development is essential for bacterial transformation since it enables bacteria to take up free DNA from the surrounding environment. The regulation of teichoic acid biosynthesis is tightly controlled during pneumococcal competence; however, the mechanism governing this regulation and its impact on transformation remains poorly understood. We demonstrated that a defect in lipoteichoic acid ligase (TacL)-mediated lipoteichoic acids (LTAs) biosynthesis was associated with impaired pneumococcal transformation. Using a fragment of tacL regulatory probe as bait in a DNA pulldown assay, we successfully identified several regulatory proteins, including ComE. Electrophoretic mobility shift assays revealed that phosphomimetic ComE, but not wild-type ComE, exhibited specific binding to the probe. DNase I footprinting assays revealed the specific binding sequences encompassing around 30 base pairs located 31 base pairs upstream from the start codon of tacL. Expression of tacL was found to be upregulated in the ΔcomE strain, and the addition of exogenous competence-stimulating peptide repressed the tacL transcription in the wild-type strain but not the ΔcomE mutant, indicating that ComE exerted a negative regulatory effect on the transcription of tacL. Mutation in the JH2 region of tacL upstream regulatory sequence led to increased LTAs abundance and displayed higher transformation efficiency. Collectively, our work identified the regulatory mechanisms that control LTAs biosynthesis during competence and thereby unveiled a repression mechanism underlying pneumococcal transformation.


Assuntos
Proteínas de Bactérias , Regulação Bacteriana da Expressão Gênica , Lipopolissacarídeos , Streptococcus pneumoniae , Ácidos Teicoicos , Transformação Bacteriana , Ácidos Teicoicos/biossíntese , Ácidos Teicoicos/metabolismo , Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Lipopolissacarídeos/biossíntese , Streptococcus pneumoniae/genética , Streptococcus pneumoniae/metabolismo , Transcrição Gênica , Regiões Promotoras Genéticas , Competência de Transformação por DNA , Mutação , Ligação Proteica , Ligases/genética , Ligases/metabolismo
6.
Angew Chem Int Ed Engl ; : e202407448, 2024 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-38782721

RESUMO

Controlling the interplay between relaxation and charge/energy transfer processes in the excited states of photocatalysts is crucial for the performance of artificial photosynthesis. Metal-to-ligand charge-transfer triplet states (3MLCT*) of ruthenium(II) complexes are broadly implemented for photocatalysis, but an effective means of managing the triplets for enhanced photocatalysis has been lacking. Herein, We proposed a strategy to considerably prolong the triplet excited-state lifetime by decorating a ruthenium(II) phosphine complex (RuP-1) with pendent polyaromatic hydrocarbons (PAHs). Systematic studies demonstrate that in RuP-4 decorated with anthracene, sub-picosecond electron transfer from anthracene to 3MLCT* leads to a charge-separated state that can mediate the formation of the intra-ligand triplet state (3IL) of anthracene, resulting in an exceptionally long excited-state up to several milliseconds. This triplet management strategy enables impressive photocatalytic reduction of CO2 to CO with a turnover number (TON) of 404, an optimized quantum yield of 43 % and 100 % selectivity, which is the highest reported performance for mononuclear photocatalysts without additional photosensitizers. RuP-4 also catalyzes photochemical hydrogen generation under argon. This work opens up an avenue for regulating the excited-state charge/energy flow for the development of long-lived 3IL multi-functional mononuclear photocatalysts to boost artificial photosynthesis.

7.
Cell Mol Biol Lett ; 29(1): 58, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38649803

RESUMO

Non-small cell lung cancer (NSCLC), characterized by low survival rates and a high recurrence rate, is a major cause of cancer-related mortality. Aberrant activation of the PI3K/AKT/mTOR signaling pathway is a common driver of NSCLC. Within this study, the inhibitory activity of (+)-anthrabenzoxocinone ((+)-ABX), an oxygenated anthrabenzoxocinone compound derived from Streptomyces, against NSCLC is demonstrated for the first time both in vitro and in vivo. Mechanistically, it is confirmed that the PI3K/AKT/mTOR signaling pathway is targeted and suppressed by (+)-ABX, resulting in the induction of S and G2/M phase arrest, apoptosis, and autophagy in NSCLC cells. Additionally, the augmentation of intracellular ROS levels by (+)-ABX is revealed, further contributing to the inhibition of the signaling pathway and exerting inhibitory effects on tumor growth. The findings presented in this study suggest that (+)-ABX possesses the potential to serve as a lead compound for the treatment of NSCLC.


Assuntos
Apoptose , Autofagia , Carcinoma Pulmonar de Células não Pequenas , Pontos de Checagem do Ciclo Celular , Neoplasias Pulmonares , Fosfatidilinositol 3-Quinases , Proteínas Proto-Oncogênicas c-akt , Transdução de Sinais , Serina-Treonina Quinases TOR , Carcinoma Pulmonar de Células não Pequenas/tratamento farmacológico , Carcinoma Pulmonar de Células não Pequenas/metabolismo , Carcinoma Pulmonar de Células não Pequenas/patologia , Serina-Treonina Quinases TOR/metabolismo , Proteínas Proto-Oncogênicas c-akt/metabolismo , Humanos , Apoptose/efeitos dos fármacos , Autofagia/efeitos dos fármacos , Neoplasias Pulmonares/tratamento farmacológico , Neoplasias Pulmonares/metabolismo , Neoplasias Pulmonares/patologia , Transdução de Sinais/efeitos dos fármacos , Fosfatidilinositol 3-Quinases/metabolismo , Animais , Linhagem Celular Tumoral , Pontos de Checagem do Ciclo Celular/efeitos dos fármacos , Camundongos Nus , Camundongos , Proliferação de Células/efeitos dos fármacos , Camundongos Endogâmicos BALB C , Ensaios Antitumorais Modelo de Xenoenxerto , Espécies Reativas de Oxigênio/metabolismo , Antineoplásicos/farmacologia
8.
Chem Rev ; 124(9): 5695-5763, 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38629390

RESUMO

The properties of colloidal quantum-confined semiconductor nanocrystals (NCs), including zero-dimensional (0D) quantum dots, 1D nanorods, 2D nanoplatelets, and their heterostructures, can be tuned through their size, dimensionality, and material composition. In their photovoltaic and photocatalytic applications, a key step is to generate spatially separated and long-lived electrons and holes by interfacial charge transfer. These charge transfer properties have been extensively studied recently, which is the subject of this Review. The Review starts with a summary of the electronic structure and optical properties of 0D-2D nanocrystals, followed by the advances in wave function engineering, a novel way to control the spatial distribution of electrons and holes, through their size, dimension, and composition. It discusses the dependence of NC charge transfer on various parameters and the development of the Auger-assisted charge transfer model. Recent advances in understanding multiple exciton generation, decay, and dissociation are also discussed, with an emphasis on multiple carrier transfer. Finally, the applications of nanocrystal-based systems for photocatalysis are reviewed, focusing on the photodriven charge separation and recombination processes that dictate the function and performance of these materials. The Review ends with a summary and outlook of key remaining challenges and promising future directions in the field.

9.
Angew Chem Int Ed Engl ; 63(25): e202403927, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38632085

RESUMO

All-inorganic metal halides with afterglow emission have attracted increasing attention due to their significantly longer afterglow duration and higher stability compared to their organic-inorganic hybrid counterparts. However, their afterglow colors have not yet reached the blue spectral region. Here, we report all-inorganic copper-doped Rb2AgBr3 single crystals with ultralong blue afterglow (>300 s) by modulating defect states through doping engineering. The introduction of copper(I) ions into Rb2AgBr3 facilitates the formation of bromine vacancies, thus increasing the density of trap states available for charge storage and enabling bright, persistent emission after ceasing the excitation. Moreover, cascade energy transfer between distinct emissive centers in the crystals results in ultra-broadband photoluminescence, not only covering the whole white light with near-unity quantum yield but also extending into the near-infrared region. This 'cocktail' of exotic light-emission properties, in conjunction with the excellent stability of copper-doped Rb2AgBr3 crystals, allowed us to demonstrate their implementation to solid-state lighting, night vision, and intelligent anti-counterfeiting.

10.
Angew Chem Int Ed Engl ; 63(26): e202403996, 2024 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-38679568

RESUMO

Decreasing perovskite nanocrystal size increases radiative recombination due to the quantum confinement effect, but also increases the Auger recombination rate which leads to carrier imbalance in the emitting layers of electroluminescent devices. Here, we overcome this trade-off by increasing the exciton effective mass without affecting the size, which is realized through the trace Cd2+ doping of formamidinium lead bromide perovskite nanocrystals. We observe an ~2.7 times increase in the exciton binding energy benefiting from a slight distortion of the [BX6]4- octahedra caused by doping in the case of that the Auger recombination rate is almost unchanged. As a result, bright color-saturated green emitting perovskite nanocrystals with a photoluminescence quantum yield of 96 % are obtained. Cd2+ doping also shifts up the energy levels of the nanocrystals, relative to the Fermi level so that heavily n-doped emitters convert into only slightly n-doped ones; this boosts the charge injection efficiency of the corresponding light-emitting diodes. The light-emitting devices based on those nanocrystals reached a high external quantum efficiency of 29.4 % corresponding to a current efficiency of 123 cd A-1, and showed dramatically improved device lifetime, with a narrow bandwidth of 22 nm and Commission Internationale de I'Eclairage coordinates of (0.20, 0.76) for color-saturated green emission for the electroluminescence peak centered at 534 nm, thus being fully compliant with the latest standard for wide color gamut displays.

11.
ACS Nano ; 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38324334

RESUMO

Magnetic impurity doping in semiconductors has emerged as an important strategy to endow exotic photophysical and magnetic properties. While most reported hosts are centrosymmetric semiconductors, doping magnetic ions into a noncentrosymmetric chiral semiconductor can offer additional control of photonic and spin polarization. In this work, we synthesized a Mn2+-doped chiral two-dimensional (2D) perovskite, Mn2+:(R-MPA)2PbBr4 (R-MPA+ = R-methyl phenethylammonium). We found that the optical activity of chiral 2D perovskites is enhanced with an increased concentration of Mn2+ ions. Additionally, efficient energy transfer from the chiral host to the Mn2+ dopants is observed. This energy transfer process gives rise to circularly polarized luminescence from the excited state of Mn2+ (4T1 → 6A1), exhibiting a photoluminescence quantum yield up to 24% and a dissymmetry factor of 11%. The exciton fine structures of undoped and Mn2+-doped (R-MPA)2PbBr4 are further studied through magnetic circular dichroism (MCD) spectroscopy. Our analysis shows that chiral organic cations lead to an exciton fine structure splitting energy as large as 5.0 meV, and the splitting is further increased upon Mn2+ doping. Our results reveal the strong impacts of molecular chirality and magnetic dopants on the exciton structures of halide perovskites.

12.
Adv Sci (Weinh) ; 11(12): e2306518, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38234238

RESUMO

Colloidal semiconductor nanoplatelets (NPLs) have emerged as low-cost and free-standing alternates of traditional quantum wells. The giant heavy- and light-hole splitting in NPLs allows for efficient optical spin injection. However, the electron spin lifetimes for prototypical CdSe NPLs are within a few picoseconds, likely limited by strong electron-hole exchange in these quantum- and dielectric-confined materials. Here how this hurdle can be overcome with engineered NPL-heterostructures is demonstrated. By constructing type-I CdSe/ZnS core/shell NPLs, dielectric screening inside the core is strongly enhanced, prolonging the electron spin polarization time (τesp) to over 30 ps (or 60 ps electron spin-flip time). Alternatively, by growing type-II CdSe/CdTe core/crown NPLs to spatially separate electron and hole wavefunctions, the electron-hole exchange is strongly suppressed, resulting in τesp as long as 300 ps at room temperature. This study not only exemplifies how the well-established synthetic chemistry of colloidal heterostructures can aid in spin dynamics control but also establishes the feasibility of room-temperature coherent spin manipulation in colloidal NPLs.

13.
Angew Chem Int Ed Engl ; 63(8): e202319969, 2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38179817

RESUMO

Most of current metal halide materials, including all inorganic and organic-inorganic hybrids, are crystalline materials with poor workability and plasticity that limit their application scope. Here, we develop a novel class of materials termed polymeric metal halides (PMHs) through introducing polycations into antimony-based metal halide materials as A-site cations. A series of PMHs with orange-yellow broadband emission and large Stokes shift originating from inorganic self-trapped excitons are successfully prepared, which meanwhile exhibit the excellent processability and formability of polymers. The versatility of these PMHs is manifested as the broad choices of polycations, the ready extension to manganese- and copper-based halides, and the tolerance to molar ratios between polycations and metal halides in the formation of PMHs. The merger of polymer chemistry and inorganic chemistry thus provides a novel generic platform for the development of metal halide functional materials.

14.
Adv Mater ; 36(7): e2308979, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38009644

RESUMO

Colloidal quantum-dot (QD) lasing is normally achieved in close-packed solid-state films, as a high QD volume fraction is required for stimulated emission to outcompete fast Auger decay of optical-gain-active multiexciton states. Here a new type of liquid optical-gain medium is demonstrated, in which compact compositionally-graded QDs (ccg-QDs) that feature strong suppression of Auger decay are liquefied using a small amount of solvent. Transient absorption measurements of ccg-QD liquid suspensions reveal broad-band optical gain spanning a wide spectral range from 560 (green) to 675 nm (red). The gain magnitude is sufficient to realize a two-color amplified spontaneous emission (ASE) at 637 and 594 nm due to the band-edge (1S) and the excited-state (1P) transition, respectively. Importantly, the ASE regime is achieved using quasicontinuous excitation with nanosecond pulses. Furthermore, the ASE is highly stable under prolonged excitation, which stands in contrast to traditional dyes that exhibit strong degradation under identical excitation conditions. These observations point toward a considerable potential of high-density ccg-QD suspensions as liquid, dye-like optical gain media that feature readily achievable spectral tunability and stable operation under intense photoexcitation.

15.
Adv Mater ; 36(6): e2309420, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38009823

RESUMO

Lead halide perovskite quantum dots (QDs) have recently emerged as a promising material platform for quantum information processing owing to their strong light-matter interaction and relatively long-lived optical and spin coherences. In particular, the coherence of the fine-structure bright excitons is sustainable up to room temperature and can be observed even at an ensemble level. Here modulation of the polarization of these excitons in CsPbI3 QDs and manipulation of their time-domain coherent dynamics using a longitudinal magnetic field are demonstrated. The manipulation is realized using femtosecond quantum beat spectroscopy performed with both circularly- and linearly-polarized pulses. The results are well captured by the density of matrix simulation and are picturized using a Bloch sphere. This study forms the basis for preparing arbitrary coherent superpositions of excitons in perovskite QDs for an array of quantum technologies under near-ambient conditions.

16.
Cell Biochem Biophys ; 82(1): 259-270, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38129709

RESUMO

Excessive aggressive migration and invasion are important factors that increase the mortality of cancer patients. Matrix metalloproteinase 13 (MMP13) expression is positively correlated with lung cancer malignancy. However, the mechanism underlying an elevated MMP13 expression is not clearly defined. In this study, we demonstrated that hypoxia induced by CoCl2 enhanced the expression of HIF1α, JAK2, STAT3 and MMP13 in A549 cells. A positive correlation between HIF1α and MMP13 expression was observed in lung adenocarcinoma patients. Mechanically, hypoxia upregulated HIF1α/JAK2/STAT3 signal axis, promoted transcription factor STAT3 to bind to MMP13 promoter region, and activated MMP13 transcription, finally promoted cell invasion and migration. However, stattic (STAT3 inhibitor) could reverse this effect caused by STAT3 in A549 cells. Together our data indicated that hypoxia might promote lung cancer cell migration and invasion through the HIF1α/JAK2/STAT3 axis by activating MMP13 transcription. MMP13 could be a promising therapeutic target for lung adenocarcinoma metastasis.


Assuntos
Adenocarcinoma de Pulmão , Neoplasias Pulmonares , Humanos , Neoplasias Pulmonares/metabolismo , Metaloproteinase 13 da Matriz/genética , Metaloproteinase 13 da Matriz/metabolismo , Hipóxia/metabolismo , Movimento Celular , Fator de Transcrição STAT3/metabolismo , Linhagem Celular Tumoral , Janus Quinase 2/metabolismo , Janus Quinase 2/farmacologia , Proliferação de Células
17.
J Transl Med ; 21(1): 898, 2023 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-38082290

RESUMO

BACKGROUND: Early microbial exposure is associate with protective allergic asthma. We have previously demonstrated that Streptococcus pneumoniae aminopeptidase N (PepN), one of the pneumococcal components, inhibits ovalbumin (OVA) -induced airway inflammation in murine models of allergic asthma, but the underlying mechanism was incompletely determined. METHODS: BALB/c mice were pretreated with the PepN protein and exposed intranasally to HDM allergen. The anti-inflammatory mechanisms were investigated using depletion and adoptive transfer experiments as well as transcriptome analysis and isolated lung CD11chigh macrophages. RESULTS: We found pretreatment of mice with PepN promoted the proliferation of lung-resident F4/80+CD11chigh macrophages in situ but also mobilized bone marrow monocytes to infiltrate lung tissue that were then transformed into CD11high macrophages. PepN pre-programmed the macrophages during maturation to an anti-inflammatory phenotype by shaping the metabolic preference for oxidative phosphorylation (OXPHOS) and also inhibited the inflammatory response of macrophages by activating AMP-activated protein kinase. Furthermore, PepN treated macrophages also exhibited high-level costimulatory signaling molecules which directed the differentiation into Treg. CONCLUSION: Our results demonstrated that the expansion of CD11chigh macrophages in lungs and the OXPHOS metabolic bias of macrophages are associated with reduced allergic airway inflammation after PepN exposure, which paves the way for its application in preventing allergic asthma.


Assuntos
Asma , Pneumonia , Camundongos , Animais , Streptococcus pneumoniae/metabolismo , Antígenos CD13 , Citocinas/metabolismo , Asma/metabolismo , Pulmão/metabolismo , Inflamação/prevenção & controle , Macrófagos/metabolismo , Anti-Inflamatórios , Fenótipo , Ovalbumina , Modelos Animais de Doenças , Camundongos Endogâmicos BALB C
18.
Front Cell Infect Microbiol ; 13: 1280372, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-38106474

RESUMO

Background: Carbapenem-resistant Acinetobacter baumannii (CRAB) has emerged as a predominant strain of healthcare-associated infections worldwide, particularly in intensive care units (ICUs). Therefore, it is imperative to study the molecular epidemiology of CRAB in the ICUs using multiple molecular typing methods to lay the foundation for the development of infection prevention and control strategies. This study aimed to determine the antimicrobial susceptibility profile, the molecular epidemiology and conduct homology analysis on CRAB strains isolated from ICUs. Methods: The sensitivity to various antimicrobials was determined using the minimum inhibitory concentration (MIC) method, Kirby-Bauer disk diffusion (KBDD), and E-test assays. Resistance genes were identified by polymerase chain reaction (PCR). Molecular typing was performed using multilocus sequence typing (MLST) and multiple-locus variable-number tandem repeat analysis (MLVA). Results: Among the 79 isolates collected, they exhibited high resistance to various antimicrobials but showed low resistance to levofloxacin, trimethoprim-sulfamethoxazole, and tetracyclines. Notably, all isolates of A. baumannii were identified as multidrug-resistant A. baumannii (MDR-AB). The bla OXA-51-like, adeJ, and adeG genes were all detected, while the detection rates of bla OXA-23-like (97.5%), adeB (93.67%), bla ADC (93.67%), qacEΔ1-sul1 (84.81%) were higher; most of the Ambler class A and class B genes were not detected. MLST analysis on the 79 isolates identified five sequence types (STs), which belonged to group 3 clonal complexes 369. ST1145Ox was the most frequently observed ST with a count of 56 out of 79 isolates (70.89%). MLST analysis for non-sensitive tigecycline isolates, which were revealed ST1145Ox and ST1417Ox as well. By using the MLVA assay, the 79 isolates could be grouped into a total of 64 distinct MTs with eleven clusters identified in them. Minimum spanning tree analysis defined seven different MLVA complexes (MCs) labeled MC1 to MC6 along with twenty singletons. The locus MLVA-AB_2396 demonstrated the highest Simpson's diversity index value at 0.829 among all loci tested in this study while also having one of the highest variety of tandem repeat species. Conclusion: The molecular diversity and clonal affinities within the genomes of the CRAB strains were clearly evident, with the identification of ST1144Ox, ST1658Ox, and ST1646Oxqaq representing novel findings.


Assuntos
Acinetobacter baumannii , Antibacterianos , Humanos , Antibacterianos/farmacologia , Antibacterianos/uso terapêutico , Acinetobacter baumannii/genética , beta-Lactamases/genética , Tipagem de Sequências Multilocus/métodos , Epidemiologia Molecular , Farmacorresistência Bacteriana/genética , Hospitais de Ensino , Testes de Sensibilidade Microbiana , China/epidemiologia , Carbapenêmicos/farmacologia , Unidades de Terapia Intensiva
19.
J Am Chem Soc ; 145(47): 25864-25873, 2023 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-37971813

RESUMO

Optical gain of colloidal quantum dots (QDs) is often attained in the multiexciton regime, which strongly complicates their lasing applications as the gain lifetime is limited by nonradiative Auger recombination occurring typically on the picosecond time scale. In principle, low-threshold gain can be achieved if the gain-active emission has a sizable red shift compared to the absorption. But, this mechanism has been rarely observed in typical QDs featuring small Stokes shift due to their weak electron-phonon coupling. Here, we report the observation of sub-single-exciton gain in CsPbI3 and CsPbBr3 perovskite QDs, which is unequivocally established through pinpointing the stimulated emission and biexciton absorption signatures using polarization-controlled femtosecond transient absorption spectroscopy. The soft lattice of perovskite QDs and hence strong electron-phonon coupling lead to two stimulated emission features from free and self-trapped excitons, respectively. In monodisperse QDs of varying sizes, the Stokes shift of the self-trapped exciton emission is sufficiently large to overcome the biexciton absorption loss and the inhomogeneous line width, enabling optical gain with average exciton occupancy down to <10%.

20.
Virulence ; : 2283898, 2023 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-37964595

RESUMO

The detoxified pneumolysin derivative ΔA146Ply has been proven to have a direct anti-triple negative breast cancer effect by our group, but its work model remains unclear. In this study, we focused on its ability to inhibit triple-negative breast cancer metastasis. We found that ΔA146Ply suppressed the migration and invasion of triple-negative breast cancer cells by activating mannose receptor and toll-like receptor 4. Their activation triggers the activation of the mammalian target of rapamycin signaling, sequentially leading to autophagy, transforming growth factor-ß1, and epithelial-mesenchymal transition inhibition. Furthermore, the combination of doxorubicin and ΔA146Ply significantly inhibited triple-negative breast cancer progression and prolonged survival in tumor-bearing mice. Taken together, our study provides an alternative microbiome-based mannose receptor-targeted therapy for triple-negative breast cancer and a novel theoretical and experimental basis for the downstream signaling pathway of the mannose receptor.

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