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1.
Proc Natl Acad Sci U S A ; 121(13): e2315407121, 2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38502699

RESUMO

Organic electrodes mainly consisting of C, O, H, and N are promising candidates for advanced batteries. However, the sluggish ionic and electronic conductivity limit the full play of their high theoretical capacities. Here, we integrate the idea of metal-support interaction in single-atom catalysts with π-d hybridization into the design of organic electrode materials for the applications of lithium (LIBs) and potassium-ion batteries (PIBs). Several types of transition metal single atoms (e.g., Co, Ni, Fe) with π-d hybridization are incorporated into the semiconducting covalent organic framework (COF) composite. Single atoms favorably modify the energy band structure and improve the electronic conductivity of COF. More importantly, the electronic interaction between single atoms and COF adjusts the binding affinity and modifies ion traffic between Li/K ions and the active organic units of COFs as evidenced by extensive in situ and ex situ characterizations and theoretical calculations. The corresponding LIB achieves a high reversible capacity of 1,023.0 mA h g-1 after 100 cycles at 100 mA g-1 and 501.1 mA h g-1 after 500 cycles at 1,000 mA g-1. The corresponding PIB delivers a high reversible capacity of 449.0 mA h g-1 at 100 mA g-1 after 150 cycles and stably cycled over 500 cycles at 1,000 mA g-1. This work provides a promising route to engineering organic electrodes.

2.
J Am Chem Soc ; 146(15): 10908-10916, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38579155

RESUMO

Self-assembly of sophisticated polyhedral cages has drawn much attention because of their elaborate structures and potential applications. Herein, we report the anion-coordination-driven assembly of the first A8L12 (A = anion, L = ligand) octanuclear cubic structures from phosphate anion and p-xylylene-spaced bis-bis(urea) ligands via peripheral templating of countercations (TEA+ or TPA+). By attaching terminal aryl rings (phenyl or naphthyl) to the ligand through a flexible (methylene) linker, these aryls actively participate in the formation of plenty of "aromatic pockets" for guest cation binding. As a result, multiple peripheral guests (up to 22) of suitable size are bound on the faces and vertices of the cube, forming a network of cation-π interactions to stabilize the cube structure. More interestingly, when chiral ligands were used, either diastereomers of mixed Λ- and Δ-configurations (with TEA+ countercation) for the phosphate coordination centers or enantiopure cubes (with TPA+) were formed. Thus, the assembly and chirality of the cube can be modulated by remote terminal groups and peripheral templating tetraalkylammonium cations.

3.
J Am Chem Soc ; 146(23): 15787-15795, 2024 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-38738985

RESUMO

The encapsulation of different guest molecules by their different recognition domains of proteins leads to selective binding, catalysis, and transportation. Synthetic hosts capable of selectively binding different guests in their different cavities to mimic the function of proteins are highly desirable but challenging. Here, we report three ladder-shaped, triple-cavity metallacages prepared by multicomponent coordination-driven self-assembly. Interestingly, the porphyrin-based metallacage is capable of heteroleptic encapsulation of fullerenes (C60 or C70) and coronene using its different cavities, allowing distinct allosteric recognition of coronene upon the addition of C60 or C70. Owing to the different binding affinities of the cavities, the metallacage hosts one C60 molecule in the central cavity and two coronene units in the side cavities, while encapsulating two C70 molecules in the side cavities and one coronene molecule in the central cavity. The rational design of multicavity assemblies that enable heteroleptic encapsulation and allosteric recognition will guide the further design of advanced supramolecular constructs with tunable recognition properties.

4.
J Am Chem Soc ; 146(32): 22797-22806, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39087792

RESUMO

The construction of isotypic high-nuclearity inorganic cages with identical pristine parent structure and increasing nuclearity is highly important for molecular growth and structure-property relationship study, yet it still remains a great challenge. Here, we provide an in situ growth approach for successfully synthesizing a series of new giant hollow polymolybdate dodecahedral cages, Mo250, Mo260-I, and Mo260-E, whose structures are growth based on giant polymolybdate cage Mo240. Remarkably, they show two pathways of nuclear growth based on Mo240, that is, the growth of 10 and 20 Mo centers on the inner and outer surfaces to afford Mo250 and Mo260-I, respectively, and the growth of 10 Mo centers both on the inner and outer surfaces to give Mo260-E. To the best of our knowledge, this is the first study to display the internal and external nuclear growth of a giant hollow polyoxometalate cage. More importantly, regular variations in structure and nuclearity confer these polymolybdate cages with different optical properties, oxidative activities, and hydrogen atom transfer effect, thus allowing them to exhibit moderate to excellent photocatalytic performance in oxidative cross-coupling reactions between different unactivated alkanes and N-heteroarenes. In particular, Mo240 and Mo260-E with better comprehensive abilities can offer the desired coupling product with yield up to 92% within 1 h.

5.
Small ; 20(24): e2308956, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38183403

RESUMO

The present study proposes a novel engineering concept for the customization of functionality and construction of superstructure to fabricate 2D monolayered N-doped carbon superstructure electrocatalysts decorated with Co single atoms or Co2P nanoparticles derived from 2D bimetallic ZnCo-ZIF superstructure precursors. The hierarchically porous carbon superstructure maximizes the exposure of accessible active sites, enhances electron/mass transport efficiency, and accelerates reaction kinetics simultaneously. Consequently, the Co single atoms embedded N-doped carbon superstructure (Co-NCS) exhibits remarkable catalytic activity toward oxygen reduction reaction, achieving a half-wave potential of 0.886 V versus RHE. Additionally, the Co2P nanoparticles embedded N-doped carbon superstructure (Co2P-NCS) demonstrates high activity for both oxygen evolution reaction and hydrogen evolution reaction, delivering low overpotentials of 292 mV at 10 mA cm-2 and 193 mV at 10 mA cm-2 respectively. Impressively, when employed in an assembled rechargeable Zn-air battery, the as-prepared 2D carbon superstructure electrocatalysts exhibit exceptional performance with a peak power density of 219 mW cm-2 and a minimal charge/discharge voltage gap of only 1.16 V at 100 mA cm-2. Moreover, the cell voltage required to drive an overall water-splitting electrolyzer at a current density of 10 mA cm-2 is merely 1.69 V using these catalysts as electrodes.

6.
Osteoporos Int ; 2024 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-39085499

RESUMO

The importance of osteoporosis assessment before lumbar surgery is well recognized. The MRI-based Vertebral Bone Quality (VBQ) score is introduced to evaluate bone quality; however, its diagnostic value has not been well documented. The purpose of this meta-analysis was to summarize the diagnostic value of the VBQ score for osteoporosis or osteopenia in patients undergoing lumbar surgery. We comprehensively searched electronic databases for studies exploring the diagnostic accuracy of the VBQ score for osteoporosis/osteopenia in patients with lumbar disease following the PRISMA guidelines. The quality of the included studies was assessed. The VBQ scores were compared between the groups, and the pooled sensitivity, specificity, and summary receiver operating characteristic (ROC) were calculated. Publication bias was assessed, and meta-regression was conducted. We included 17 studies with a total of 2815 patients, with a mean age of 66.4 years and a percentage of females of 72.5%. According to the QUADAS-2 tool, the quality of the included studies was relatively high. The results showed a significantly higher VBQ score in the osteoporosis/osteopenia group compared with the control group. According to the mean VBQ cutoff value of 3.02 ± 0.38 for the diagnosis of osteoporosis, the pooled sensitivity and specificity were 0.76 and 0.74, respectively, and the AUC was 0.81. According to the mean VBQ cutoff value of 2.31 ± 0.18 for the diagnosis of osteopenia, the pooled sensitivity and specificity were 0.78 and 0.58, respectively, and the AUC was 0.76. The MRI-based VBQ score could provide useful information for identifying patients with low bone mass who need further evaluation. Future prospective studies are still needed to evaluate the complementary role of the VBQ score.

7.
Phys Rev Lett ; 132(1): 010602, 2024 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-38242678

RESUMO

As a hybrid of artificial intelligence and quantum computing, quantum neural networks (QNNs) have gained significant attention as a promising application on near-term, noisy intermediate-scale quantum devices. Conventional QNNs are described by parametrized quantum circuits, which perform unitary operations and measurements on quantum states. In this Letter, we propose a novel approach to enhance the expressivity of QNNs by incorporating randomness into quantum circuits. Specifically, we introduce a random layer, which contains single-qubit gates sampled from a trainable ensemble pooling. The prediction of QNN is then represented by an ensemble average over a classical function of measurement outcomes. We prove that our approach can accurately approximate arbitrary target operators using Uhlmann's theorem for majorization, which enables observable learning. Our proposal is demonstrated with extensive numerical experiments, including observable learning, Rényi entropy measurement, and image recognition. We find the expressivity of QNNs is enhanced by introducing randomness for multiple learning tasks, which could have broad application in quantum machine learning.

8.
Anesthesiology ; 141(1): 100-115, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38537025

RESUMO

BACKGROUND: Although it has been established that elevated blood pressure and its variability worsen outcomes in spontaneous intracerebral hemorrhage, antihypertensives use during the acute phase still lacks robust evidence. A blood pressure-lowering regimen using remifentanil and dexmedetomidine might be a reasonable therapeutic option given their analgesic and antisympathetic effects. The objective of this superiority trial was to validate the efficacy and safety of this blood pressure-lowering strategy that uses remifentanil and dexmedetomidine in patients with acute intracerebral hemorrhage. METHODS: In this multicenter, prospective, single-blinded, superiority randomized controlled trial, patients with intracerebral hemorrhage and systolic blood pressure (SBP) 150 mmHg or greater were randomly allocated to the intervention group (a preset protocol with a standard guideline management using remifentanil and dexmedetomidine) or the control group (standard guideline-based management) to receive blood pressure-lowering treatment. The primary outcome was the SBP control rate (less than 140 mmHg) at 1 h posttreatment initiation. Secondary outcomes included blood pressure variability, neurologic function, and clinical outcomes. RESULTS: A total of 338 patients were allocated to the intervention (n = 167) or control group (n = 171). The SBP control rate at 1 h posttreatment initiation in the intervention group was higher than that in controls (101 of 161, 62.7% vs. 66 of 166, 39.8%; difference, 23.2%; 95% CI, 12.4 to 34.1%; P < 0.001). Analysis of secondary outcomes indicated that patients in the intervention group could effectively reduce agitation while achieving lighter sedation, but no improvement in clinical outcomes was observed. Regarding safety, the incidence of bradycardia and respiratory depression was higher in the intervention group. CONCLUSIONS: Among intracerebral hemorrhage patients with a SBP 150 mmHg or greater, a preset protocol using a remifentanil and dexmedetomidine-based standard guideline management significantly increased the SBP control rate at 1 h posttreatment compared with the standard guideline-based management.


Assuntos
Anti-Hipertensivos , Pressão Sanguínea , Hemorragia Cerebral , Dexmedetomidina , Remifentanil , Humanos , Dexmedetomidina/uso terapêutico , Dexmedetomidina/administração & dosagem , Remifentanil/administração & dosagem , Remifentanil/uso terapêutico , Masculino , Feminino , Estudos Prospectivos , Hemorragia Cerebral/tratamento farmacológico , Idoso , Pessoa de Meia-Idade , Método Simples-Cego , Pressão Sanguínea/efeitos dos fármacos , Anti-Hipertensivos/uso terapêutico , Anti-Hipertensivos/administração & dosagem , Resultado do Tratamento , Hipnóticos e Sedativos/uso terapêutico
9.
Fish Shellfish Immunol ; 145: 109356, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38163495

RESUMO

DM9-containing protein in invertebrates functions as pattern recognition receptor (PRR) to play significant roles in innate immunity. In the present study, a novel DM9-containg protein (defined as EsDM9CP-1) was identified from the Chinese mitten crab Eriocheir sinensis. EsDM9CP-1 is composed of 330 amino acids containing a Methyltransf_FA domain and two tandem DM9 repeats. The deduced amino acid sequence of EsDM9CP-1 shared low similarity with the previously identified DM9CPs from other species, and it was closely clustered with Platyhelminthes DM9CPs and then assigned into the branch of invertebrate DM9CPs in the unrooted phylogenetic tree. The mRNA transcripts of EsDM9CP-1 were highly expressed in haemocytes, gill, and heart. After Aeromonas hydrophila stimulation, the expression levels of EsDM9CP-1 mRNA in haemocytes increased significantly at 3 h (3.88-fold, p < 0.05) and 6 h (2.71-fold, p < 0.05), compared with that of PBS group, respectively. EsDM9CP-1 protein was mainly distributed in the cytoplasm and membrane of haemocytes. The recombinant EsDM9CP-1 protein (rEsDM9CP-1) exhibited binding affinity to MAN, PGN, LPS and Poly (I:C), and also to Gram-positive bacteria (Staphylococcus aureus, Micrococcus luteus and Bacillus subtilis), Gram-negative bacteria (Escherichia coli, A. hydrophila and Vibrio splendidus) and fungi (Pichia pastoris and Metschnikowia bicuspidata) in a Ca2+-dependent manner. It was able to agglutinate A. hydrophila, S. aureus, M. luteus, M. bicuspidata and P. pastoris, and inhibit the growth of A. hydrophila and M. bicuspidate. These results suggested that EsDM9CP-1 in crab not only functioned as a PRR, but also agglutinated and inhibited the growth of microbes.


Assuntos
Braquiúros , Staphylococcus aureus , Humanos , Animais , Filogenia , Staphylococcus aureus/metabolismo , Sequência de Bases , Receptores de Reconhecimento de Padrão/genética , Imunidade Inata/genética , RNA Mensageiro/metabolismo , Braquiúros/genética , Hemócitos
10.
Nanotechnology ; 35(13)2024 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-38134437

RESUMO

Due to the unique ability to mimic natural enzymes, single-atom nanoenzymes (SAE) have garnered significant attention and research in tumor therapy. However, their efficacy often faces challenges in terms of drug delivery methods, and the research regarding their applications in radiotherapy is scarce. Herein, we introduce a light-controlled SAE hydrogel platform (SH) for glutathione-depletion-mediated low-dose radiotherapy. The SH incorporates a Cu single-atom enzyme (CuSA), and upon irradiation with 1064 nm near-infrared light, the CuSA can convert light energy into heat, which in turn degrades the hydrogel, enabling the release of CuSA into tumor cells or tissues. The diffused CuSA not only can facilitate the conversion of H2O2into hydroxyl radicals (•OH), but also can effectively depletes cellular glutathione. This leads to increased sensitivity of tumor cells to radiotherapy, resulting in enhanced cytotoxicity even at low doses. The animal study results further confirmed the good tumor-killing efficacy of this SH system. To the best of our knowledge, this stands as the pioneering report on leveraging a single-atom enzyme for GSH depletion-mediated low-dose radiotherapy.


Assuntos
Sistemas de Liberação de Medicamentos , Neoplasias , Animais , Difusão , Glutationa , Temperatura Alta , Hidrogéis , Peróxido de Hidrogênio
11.
Anim Biotechnol ; 35(1): 2380766, 2024 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-39034460

RESUMO

Increasing the number of teats in sheep helps to improve the survival rate of sheep lambs after birth. In order to analyze the candidate genes related to the formation of multiple teats in Hu sheep, the present study was conducted to investigate the genetic pattern of multiple teats in Hu sheep. In this study, based on genome-wide data from 157 Hu sheep, Fst, xp-EHH, Pi and iHS signaling were performed, and the top 5% signal regions of each analyzed result were annotated based on the Oar_v4.0 for sheep. The results show that a total of 142 SNP loci were selected. We found that PTPRG, TMEM117 and LRP1B genes were closely associated with polypodium formation in Hu sheep, in addition, among the candidate genes related to polypodium we found genes such as TMEM117, SLC25A21 and NCKAP5 related to milk traits. The present study screened out candidate genes for the formation of multiple teats at the genomic level in Hu sheep.


Assuntos
Polimorfismo de Nucleotídeo Único , Animais , Ovinos/genética , Polimorfismo de Nucleotídeo Único/genética , Feminino , Estudo de Associação Genômica Ampla/veterinária
12.
J Dairy Sci ; 2024 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-38851580

RESUMO

Inhibition of methyl-coenzyme M reductase can suppress the activity of ruminal methanogens, thereby reducing enteric methane emissions of ruminants. However, developing specific and environmentally friendly inhibitors is a challenging endeavor. To identify a natural and effective methane inhibitor that specifically targets methyl-coenzyme M reductase, molecular docking technology was employed to screen a library of phytogenic compounds. A total of 52 candidate compounds were obtained through molecular docking technique. Rosmarinic acid (RA) was one of the compounds that could traverse a narrow channel and bind to the active sites of methyl-coenzyme M reductase, with a calculated binding free energy of -9.355 kcal/mol. Furthermore, the effects of rosmarinic acid supplementation on methane production, rumen fermentation, and the microorganism's community in dairy cows were investigated through in vitro rumen fermentation simulations according to a random design. Supplementation of RA resulted in a 15% decrease in methane production compared with the control. In addition, RA increased the molar proportion of acetate and propionate, whereas the sum of acetate and butyrate divided by propionate was decreased. At the bacterial level, the relative abundance of Rikenellaceae RC9 gut group, Christensenellaceae R7 group, Candidatus Saccharimonas, Desulfovibrio, and Lachnospiraceae FE2018 group decreased with RA supplementation. Conversely, the addition of RA significantly increased the relative abundance of DNF00809 (a genus from Eggerthellaceae), Denitrobacterium, an unclassified genus from Eggerthellaceae, an unclassified genus from Bacteroidales, and an unclassified genus from Atopobiaceae. At the archaeal level, the relative abundance of Methanobrevibacter decreased, while that of Methanosphaera increased with the RA supplementation. These findings suggested that RA has the potential to be used as a novel natural additive for inhibiting ruminal methane production.

13.
J Acoust Soc Am ; 155(6): 3774-3781, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38860835

RESUMO

It is known that total absorption of flexural waves in a thin beam is possible through the use of monopole-dipole scatterers. In this study, we introduce a pair of identical monopole scatterers for near-total absorption of flexural waves in a thin and wide beam. Despite the two scatterers being both of the monopole type, the resonant modes of the scatterer pair exhibit monopole and dipole properties. By selecting the proper width for the beam, the two resonant modes degenerate, which leads to the total absorption. Although the beam is considerably wide, the frequency range of interest remains below the cut-on frequency of the n = 1 propagating mode, ensuring one-dimensional flexural wave propagation. Further simulations and theoretical analysis revealed that the degeneracy of the monopole and dipole modes results from their interaction with a higher-order localized flexural mode. The simulation results demonstrate absorption exceeding 99%, complemented by experimental data showing approximately 90% absorption.

14.
Sensors (Basel) ; 24(15)2024 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-39123993

RESUMO

Three-section landslides are renowned for their immense size, concealed development process, and devastating impact. This study conducted physical model tests to simulate one special geological structure called a three-section-within landslide. The failure process and precursory characteristics of the tested samples were meticulously analyzed using video imagery, micro-seismic (MS) signals, and acoustic emission (AE) signals, with a focus on event activity, intensity, and frequency. A novel classification method based on AE waveform characteristics was proposed, categorizing AE signals into burst signals and continuous signals. The findings reveal distinct differences in the evolution of these signals. Burst signals appeared exclusively during the crack propagation and failure stages. During these stages, the cumulative AE hits of burst signals increased gradually, with amplitude rising and then declining. High-amplitude burst signals were predominantly distributed in the middle- and high-frequency bands. In contrast, cumulative AE hits of continuous signals escalated rapidly, with amplitude monotonously increasing, and high-amplitude continuous signals were primarily distributed in the low-frequency band. The emergence of burst signals and high-frequency AE signals indicated the generation of microcracks, serving as early-warning indicators. Notably, the early-warning points of AE signals were detected earlier than those of video imagery and MS signals. Furthermore, the early-warning point of burst signals occurred earlier than those of continuous signals, and the early-warning point of the classification method preceded that of overall AE signals.

15.
Int J Mol Sci ; 25(9)2024 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-38732079

RESUMO

Long-term spaceflight is known to induce disruptions in circadian rhythms, which are driven by a central pacemaker located in the suprachiasmatic nucleus (SCN) of the hypothalamus, but the underlying molecular mechanisms remain unclear. Here, we developed a rat model that simulated microgravity and isolation environments through tail suspension and isolation (TSI). We found that the TSI environment imposed circadian disruptions to the core body temperature, heart rate, and locomotor-activity rhythms of rats, especially in the amplitude of these rhythms. In TSI model rats' SCNs, the core circadian gene NR1D1 showed higher protein but not mRNA levels along with decreased BMAL1 levels, which indicated that NR1D1 could be regulated through post-translational regulation. The autophagosome marker LC3 could directly bind to NR1D1 via the LC3-interacting region (LIR) motifs and induce the degradation of NR1D1 in a mitophagy-dependent manner. Defects in mitophagy led to the reversal of NR1D1 degradation, thereby suppressing the expression of BMAL1. Mitophagy deficiency and subsequent mitochondrial dysfunction were observed in the SCN of TSI models. Urolithin A (UA), a mitophagy activator, demonstrated an ability to enhance the amplitude of core body temperature, heart rate, and locomotor-activity rhythms by prompting mitophagy induction to degrade NR1D1. Cumulatively, our results demonstrate that mitophagy exerts circadian control by regulating NR1D1 degradation, revealing mitophagy as a potential target for long-term spaceflight as well as diseases with SCN circadian disruption.


Assuntos
Fatores de Transcrição ARNTL , Ritmo Circadiano , Mitofagia , Membro 1 do Grupo D da Subfamília 1 de Receptores Nucleares , Animais , Ratos , Ritmo Circadiano/fisiologia , Masculino , Fatores de Transcrição ARNTL/metabolismo , Fatores de Transcrição ARNTL/genética , Membro 1 do Grupo D da Subfamília 1 de Receptores Nucleares/metabolismo , Membro 1 do Grupo D da Subfamília 1 de Receptores Nucleares/genética , Simulação de Ausência de Peso , Núcleo Supraquiasmático/metabolismo , Núcleo Supraquiasmático/fisiologia , Proteínas Associadas aos Microtúbulos/metabolismo , Proteínas Associadas aos Microtúbulos/genética , Temperatura Corporal , Frequência Cardíaca , Ratos Sprague-Dawley , Proteólise
16.
Entropy (Basel) ; 26(7)2024 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-39056957

RESUMO

Metro stray currents flowing into transformer-neutral points cause the high neutral DC and a transformer to operate in the DC bias state.Because neutral DC caused by stray current varies with time, the neutral DC value cannot be used as the only characteristic indicator to evaluate the DC bias risk level. Thus, unified characteristic extraction and assessment methods are proposed to evaluate the DC bias risk of a transformer caused by stray current, considering the signals of transformer-neutral DC and vibration. In the characteristic extraction method, the primary characteristics are obtained by comparing the magnitude and frequency distributions of transformer-neutral DC and vibration with and without metro stray current invasion. By analyzing the correlation coefficients, the final characteristics are obtained by clustering the primary characteristics with high correlation. Then, the magnitude and frequency characteristics are extracted and used as indicators to evaluate the DC bias risk. Moreover, to avoid the influence of manual experience on indicator weights, the entropy weight method (EWM) is used to establish the assessment model. Finally, the proposed methods are applied based on the neutral DC and vibration test data of a certain transformer. The results show that the characteristic indicators can be extracted, and the transformer DC bias risk can be evaluated by using the proposed methods.

17.
Angew Chem Int Ed Engl ; 63(33): e202408016, 2024 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-38828671

RESUMO

Expanding the diversity of multi-macrocyclic nanocarbons, particularly those with all-benzene scaffolds, represents intriguing yet challenging synthetic tasks. Complementary to the existing synthetic approaches, here we report an efficient and modular post-functionalization strategy that employs iridium-catalyzed C-H borylation of the highly strained meta-cycloparaphenylenes (mCPPs) and an mCPP-derived catenane. Based on the functionalized macrocyclic synthons, a number of novel all-benzene topological structures including linear and cyclic chains, polycatenane, and pretzelane have been successfully prepared and characterized, thereby showcasing the synthetic utility and potential of the post-functionalization strategy.

18.
Angew Chem Int Ed Engl ; : e202410710, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38949854

RESUMO

Metallo-supramolecular cages have garnered tremendous attention for their diverse yet molecular-level precision structures. However, the physical properties of these supramolecular ensembles, which are of potential significance in molecular electronics, remain largely unexplored. We herein constructed a series of octahedral metallo-cages and cage-fullerene complexes with notably enhanced structural stability. As such, we could systematically evaluate the electrical conductivity of these ensembles at both the single-molecule level and aggregated bulk state (as well-defined films). Our findings reveal that counteranions and fullerene guests play a pivotal role in determining the electrical conductivity of the aggregated state, while such effects are less significant for single-molecule conductance. Both the counteranions and fullerenes effectively tune the electronic structures and packing density of metallo-supramolecular assemblies, and facilitate efficient charge transfer between the cage hosts and fullerenes, resulting in a notable one order of magnitude increase in the electrical conductivity of the aggregated state.

19.
Angew Chem Int Ed Engl ; : e202414072, 2024 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-39152651

RESUMO

Biomolecular machines autonomously convert energy into functions, driving systems away from thermodynamic equilibrium. This energy conversion is achieved by leveraging complex, kinetically asymmetric chemical reaction networks that are challenging to characterize precisely. In contrast, all known synthetic molecular systems in which kinetic asymmetry has been quantified are well described by simple single-cycle networks. Here, we report on a unique light-driven [2]rotaxane that enables the autonomous operation of a synthetic molecular machine with a multi-cycle chemical reaction network. Unlike all prior systems, the present one exploits a photoactive macrocycle, which features a different photoreactivity depending on the binding sites at which it resides. Furthermore, E to Z isomerization reverses the relative affinity of the macrocycle for two binding sites on the axle, resulting in a multi-cycle network. Building on the most recent theoretical advancements, this work quantifies kinetic asymmetry in a multi-cycle network for the first time. Our findings represent the simplest rotaxane capable of autonomous shuttling developed so far and offer a general strategy to generate and quantify kinetic asymmetry beyond single-cycle systems.

20.
Angew Chem Int Ed Engl ; 63(11): e202400049, 2024 03 11.
Artigo em Inglês | MEDLINE | ID: mdl-38193338

RESUMO

Photodynamic therapy (PDT), as an emerging cancer treatment, requires the development of highly desirable photosensitizers (PSs) with integrated functional groups to achieve enhanced therapeutic efficacy. Coordination-driven self-assembly (CDSA) would provide an alternative approach for combining multiple PSs synergistically. Here, we demonstrate a simple yet powerful strategy of combining conventional chromophores (tetraphenylethylene, porphyrin, or Zn-porphyrin) with pyridinium salt PSs together through condensation reactions, followed by CDSA to construct a series of novel metallo-supramolecular PSs (S1-S3). The generation of reactive oxygen species (ROS) is dramatically enhanced by the direct combination of two different PSs, and further reinforced in the subsequent ensembles. Among all the ensembles, S2 with two porphyrin cores shows the highest ROS generation efficiency, specific interactions with lysosome, and strong emission for probing cells. Moreover, the cellular and living experiments confirm that S2 has excellent PDT efficacy, biocompatibility, and biosafety. As such, this study will enable the development of more efficient PSs with potential clinical applications.


Assuntos
Neoplasias , Fotoquimioterapia , Porfirinas , Humanos , Fármacos Fotossensibilizantes/uso terapêutico , Espécies Reativas de Oxigênio , Porfirinas/farmacologia , Porfirinas/uso terapêutico , Neoplasias/tratamento farmacológico
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