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Pathogen infection and tissue injury are universal insults that disrupt homeostasis. Innate immunity senses microbial infections and induces cytokines/chemokines to activate resistance mechanisms. Here, we show that, in contrast to most pathogen-induced cytokines, interleukin-24 (IL-24) is predominately induced by barrier epithelial progenitors after tissue injury and is independent of microbiome or adaptive immunity. Moreover, Il24 ablation in mice impedes not only epidermal proliferation and re-epithelialization but also capillary and fibroblast regeneration within the dermal wound bed. Conversely, ectopic IL-24 induction in the homeostatic epidermis triggers global epithelial-mesenchymal tissue repair responses. Mechanistically, Il24 expression depends upon both epithelial IL24-receptor/STAT3 signaling and hypoxia-stabilized HIF1α, which converge following injury to trigger autocrine and paracrine signaling involving IL-24-mediated receptor signaling and metabolic regulation. Thus, parallel to innate immune sensing of pathogens to resolve infections, epithelial stem cells sense injury signals to orchestrate IL-24-mediated tissue repair.
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Citocinas , Ferimentos e Lesões , Animais , Camundongos , Imunidade Adaptativa , Quimiocinas , Epiderme , Imunidade Inata , Ferimentos e Lesões/imunologiaRESUMO
Billions of cells are eliminated daily from our bodies1-4. Although macrophages and dendritic cells are dedicated to migrating and engulfing dying cells and debris, many epithelial and mesenchymal tissue cells can digest nearby apoptotic corpses1-4. How these non-motile, non-professional phagocytes sense and eliminate dying cells while maintaining their normal tissue functions is unclear. Here we explore the mechanisms that underlie their multifunctionality by exploiting the cyclical bouts of tissue regeneration and degeneration during hair cycling. We show that hair follicle stem cells transiently unleash phagocytosis at the correct time and place through local molecular triggers that depend on both lipids released by neighbouring apoptotic corpses and retinoids released by healthy counterparts. We trace the heart of this dual ligand requirement to RARγ-RXRα, whose activation enables tight regulation of apoptotic cell clearance genes and provides an effective, tunable mechanism to offset phagocytic duties against the primary stem cell function of preserving tissue integrity during homeostasis. Finally, we provide functional evidence that hair follicle stem cell-mediated phagocytosis is not simply redundant with professional phagocytes but rather has clear benefits to tissue fitness. Our findings have broad implications for other non-motile tissue stem or progenitor cells that encounter cell death in an immune-privileged niche.
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Apoptose , Folículo Piloso , Homeostase , Fagocitose , Regeneração , Células-Tronco , Animais , Feminino , Masculino , Camundongos , Folículo Piloso/citologia , Folículo Piloso/metabolismo , Folículo Piloso/patologia , Ligantes , Fagócitos/citologia , Fagócitos/metabolismo , Células-Tronco/citologia , Células-Tronco/metabolismo , Retinoides/metabolismo , Metabolismo dos Lipídeos , Receptor gama de Ácido Retinoico/metabolismo , Receptor X Retinoide alfa/metabolismoRESUMO
Squamous cell carcinomas are triggered by marked elevation of RAS-MAPK signalling and progression from benign papilloma to invasive malignancy1-4. At tumour-stromal interfaces, a subset of tumour-initiating progenitors, the cancer stem cells, obtain increased resistance to chemotherapy and immunotherapy along this pathway5,6. The distribution and changes in cancer stem cells during progression from a benign state to invasive squamous cell carcinoma remain unclear. Here we show in mice that, after oncogenic RAS activation, cancer stem cells rewire their gene expression program and trigger self-propelling, aberrant signalling crosstalk with their tissue microenvironment that drives their malignant progression. The non-genetic, dynamic cascade of intercellular exchanges involves downstream pathways that are often mutated in advanced metastatic squamous cell carcinomas with high mutational burden7. Coupling our clonal skin HRASG12V mouse model with single-cell transcriptomics, chromatin landscaping, lentiviral reporters and lineage tracing, we show that aberrant crosstalk between cancer stem cells and their microenvironment triggers angiogenesis and TGFß signalling, creating conditions that are conducive for hijacking leptin and leptin receptor signalling, which in turn launches downstream phosphoinositide 3-kinase (PI3K)-AKT-mTOR signalling during the benign-to-malignant transition. By functionally examining each step in this pathway, we reveal how dynamic temporal crosstalk with the microenvironment orchestrated by the stem cells profoundly fuels this path to malignancy. These insights suggest broad implications for cancer therapeutics.
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Carcinoma de Células Escamosas , Genes ras , Células-Tronco Neoplásicas , Transdução de Sinais , Microambiente Tumoral , Proteínas ras , Animais , Camundongos , Carcinoma de Células Escamosas/genética , Carcinoma de Células Escamosas/metabolismo , Carcinoma de Células Escamosas/patologia , Leptina/metabolismo , Células-Tronco Neoplásicas/metabolismo , Células-Tronco Neoplásicas/patologia , Neovascularização Patológica , Fosfatidilinositol 3-Quinases/metabolismo , Proteínas Proto-Oncogênicas c-akt/metabolismo , Proteínas ras/genética , Proteínas ras/metabolismo , Fator de Crescimento Transformador beta/metabolismoRESUMO
The paradigmatic example of a topological phase of matter, the two-dimensional Chern insulator1-5, is characterized by a topological invariant consisting of a single integer, the scalar Chern number. Extending the Chern insulator phase from two to three dimensions requires generalization of the Chern number to a three-vector6,7, similar to the three-dimensional (3D) quantum Hall effect8-13. Such Chern vectors for 3D Chern insulators have never been explored experimentally. Here we use magnetically tunable 3D photonic crystals to achieve the experimental demonstration of Chern vectors and their topological surface states. We demonstrate Chern vector magnitudes of up to six, higher than all scalar Chern numbers previously realized in topological materials. The isofrequency contours formed by the topological surface states in the surface Brillouin zone form torus knots or links, whose characteristic integers are determined by the Chern vectors. We demonstrate a sample with surface states forming a (2, 2) torus link or Hopf link in the surface Brillouin zone, which is topologically distinct from the surface states of other 3D topological phases. These results establish the Chern vector as an intrinsic bulk topological invariant in 3D topological materials, with surface states possessing unique topological characteristics.
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Through recurrent bouts synchronous with the hair cycle, quiescent melanocyte stem cells (McSCs) become activated to generate proliferative progeny that differentiate into pigment-producing melanocytes. The signaling factors orchestrating these events remain incompletely understood. Here, we use single-cell RNA sequencing with comparative gene expression analysis to elucidate the transcriptional dynamics of McSCs through quiescence, activation, and melanocyte maturation. Unearthing converging signs of increased WNT and BMP signaling along this progression, we endeavored to understand how these pathways are integrated. Employing conditional lineage-specific genetic ablation studies in mice, we found that loss of BMP signaling in the lineage leads to hair graying due to a block in melanocyte maturation. We show that interestingly, BMP signaling functions downstream from activated McSCs and maintains WNT effector, transcription factor LEF1. Employing pseudotime analysis, genetics, and chromatin landscaping, we show that following WNT-mediated activation of McSCs, BMP and WNT pathways collaborate to trigger the commitment of proliferative progeny by fueling LEF1- and MITF-dependent differentiation. Our findings shed light upon the signaling interplay and timing of cues that orchestrate melanocyte lineage progression in the hair follicle and underscore a key role for BMP signaling in driving complete differentiation.
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Proteínas Morfogenéticas Ósseas/fisiologia , Diferenciação Celular/genética , Melanócitos/citologia , Transdução de Sinais/genética , Células-Tronco/citologia , Animais , Linhagem da Célula/genética , Perfilação da Expressão Gênica , Fator 1 de Ligação ao Facilitador Linfoide/metabolismo , Camundongos , Fator de Transcrição Associado à Microftalmia/metabolismo , Análise de Célula ÚnicaRESUMO
ConspectusMetal-organic frameworks (MOFs) represent a sophisticated blend of inorganic and organic components, promoting the development of coordination chemistry greatly and offering a versatile platform for tailored functionalities. By combining various metal nodes, organic linkers, and functional guests, MOFs provide numerous pathways for their design, synthesis, and customization. Among these, sequential linker installation (SLI) stands out as a novel and crucial strategy, enabling the precise integration of desired properties and functions at the atomic scale. SLI enhances structural diversity and stability while facilitating the meticulous construction of robust frameworks by leveraging open metal sites and functional organic linkers at targeted locations. Compared to the direct synthesis of MOFs, postsynthetic modification methods allow for precise regulation of their structures and corresponding properties. While unlike conventional postsynthetic modification methods, SLI requires the careful selection of linkers and framework design to ensure precise positioning for installation, which gives rise to the well-designed and ordered positions for the installed linkers, confirmed directly by X-ray diffraction technology.Recent advancements in MOF synthesis have led to the creation of increasingly tailored flexible matrix structures, particularly due to the diverse connection modes of multicore metal clusters, especially for the Zr6 cluster. The spatial hindrance of certain ligands has resulted in the formation of unsaturated metal clusters and various missing linker pockets. Examples of these advanced MOFs include PCN-606, PCN-608, PCN-609, PCN-700, and PCN-808, which feature specific open metal sites and certain framework flexibility conducive to SLI. Strategically positioned open metal sites within these frameworks serve as predetermined anchor points for desired functional molecules, while the frameworks' flexibility can accommodate molecules of varying sizes to a certain extent, enlarging the scopes of application greatly. This precise positioning of functional groups enables the creation of tailored sites for enhanced applications, such as adsorption, catalysis, and recognition.In this Account, we delve into the intricate process of designing and synthesizing MOFs with appropriate missing-linker pockets for the aforementioned applications. We discuss the meticulous selection of functional linkers and the methods used to insert them into the corresponding missing-linker pockets within the MOFs. Additionally, we explore the diverse properties and functionalities of the resulting MOFs, focusing on their adsorptive, catalytic, and recognition performance. Furthermore, we provide insights into the future trajectory of SLI methods, complemented by our recent works. This Account not only reviews the evolution of the SLI method but also underscores its practical applications across various functional domains, paving a rational pathway for the future development of advanced multifunctional MOFs through this method.
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Confining photons in a finite volume is highly desirable in modern photonic devices, such as waveguides, lasers and cavities. Decades ago, this motivated the study and application of photonic crystals, which have a photonic bandgap that forbids light propagation in all directions1-3. Recently, inspired by the discoveries of topological insulators4,5, the confinement of photons with topological protection has been demonstrated in two-dimensional (2D) photonic structures known as photonic topological insulators6-8, with promising applications in topological lasers9,10 and robust optical delay lines11. However, a fully three-dimensional (3D) topological photonic bandgap has not been achieved. Here we experimentally demonstrate a 3D photonic topological insulator with an extremely wide (more than 25 per cent bandwidth) 3D topological bandgap. The composite material (metallic patterns on printed circuit boards) consists of split-ring resonators (classical electromagnetic artificial atoms) with strong magneto-electric coupling and behaves like a 'weak' topological insulator (that is, with an even number of surface Dirac cones), or a stack of 2D quantum spin Hall insulators. Using direct field measurements, we map out both the gapped bulk band structure and the Dirac-like dispersion of the photonic surface states, and demonstrate robust photonic propagation along a non-planar surface. Our work extends the family of 3D topological insulators from fermions to bosons and paves the way for applications in topological photonic cavities, circuits and lasers in 3D geometries.
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Perfluorooctanoic acid (PFOA) is an environmental contaminant ubiquitous in water resources, which as a xenobiotic and carcinogenic agent, severely endangers human health. The development of techniques for its efficient removal is therefore highly sought after. Herein, we demonstrate an unprecedented zirconium-based MOF (PCN-999) possessing Zr6 and biformate-bridged (Zr6)2 clusters simultaneously, which exhibits an exceptional PFOA uptake of 1089 mg/g (2.63 mmol/g), representing a ca. 50% increase over the previous record for MOFs. Single-crystal X-ray diffraction studies and computational analysis revealed that the (Zr6)2 clusters offer additional open coordination sites for hosting PFOA. The coordinated PFOAs further enhance the interaction between coordinated and free PFOAs for physical adsorption, boosting the adsorption capacity to an unparalleled high standard. Our findings represent a major step forward in the fundamental understanding of the MOF-based PFOA removal mechanism, paving the way toward the rational design of next-generation adsorbents for per- and polyfluoroalkyl substance (PFAS) removal.
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Construction of robust heterogeneous catalysts with atomic precision is a long-sought pursuit in the catalysis field due to its fundamental significance in taming chemical transformations. Herein, we present the synthesis of a single-crystalline pyrazolate metal-organic framework (MOF) named PCN-300, bearing a lamellar structure with two distinct Cu centers and one-dimensional (1D) open channels when stacked. PCN-300 exhibits exceptional stability in aqueous solutions across a broad pH range from 1 to 14. In contrast, its monomeric counterpart assembled through hydrogen bonding displays limited stability, emphasizing the role of Cu-pyrazolate coordination bonds in framework robustness. Remarkably, the synergy of the 1D open channels, excellent stability, and the active Cu-porphyrin sites endows PCN-300 with outstanding catalytic activity in the cross dehydrogenative coupling reaction to form the C-O bond without the "compulsory" ortho-position directing groups (yields up to 96%), outperforming homogeneous Cu-porphyrin catalysts. Moreover, PCN-300 exhibits superior recyclability and compatibility with various phenol substrates. Control experiments reveal the synergy between the Cu-porphyrin center and framework in PCN-300 and computations unveil the free radical pathway of the reaction. This study highlights the power of robust pyrazolate MOFs in directly activating C-H bonds and catalyzing challenging chemical transformations in an environmentally friendly manner.
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Linker installation is a potent strategy for integrating specific properties and functionalities into metal-organic frameworks (MOFs). This method enhances the structural diversity of frameworks and enables the precise construction of robust structures, complementing the conventional postsynthetic modification approaches, by fully leveraging open metal sites and active organic linkers at targeting locations. Herein, we demonstrated an insertion of a d-camphorate linker into a flexible Zr-based MOF, PCN-700, through linker installation. The resultant homochiral MOF not only exhibits remarkable stability but also functions as a highly efficient luminescent material for enantioselective sensing. Competitive absorption and energy/electron transfer processes contribute to the sensing performance, while the difference in binding affinities dominates the enantioselectivity. This work presents a straightforward route to crafting stable homochiral MOFs for enantioselective sensing.
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3D metal-organic frameworks (MOFs) have gained attention as heterogeneous photocatalysts due to their porosity and unique host-guest interactions. Despite their potential, MOFs face challenges, such as inefficient mass transport and limited light penetration in photoinduced energy transfer processes. Recent advancements in organic photocatalysis have uncovered a variety of photoactive cores, while their heterogenization remains an underexplored area with great potential to build MOFs. This gap is bridged by incorporating photoactive cores into 2D MOF nanosheets, a process that merges the realms of small-molecule photochemistry and MOF chemistry. This approach results in recyclable heterogeneous photocatalysts that exhibit an improved mass transfer efficiency. This research demonstrates a bottom-up synthetic method for embedding photoactive cores into 2D MOF nanosheets, successfully producing variants such as PCN-641-NS, PCN-643-NS, and PCN-644-NS. The synthetic conditions were systematically studied to optimize the crystallinity and morphology of these 2D MOF nanosheets. Enhanced host-guest interactions in these 2D structures were confirmed through various techniques, particularly solid-state NMR studies. Additionally, the efficiency of photoinduced energy transfer in these nanosheets was evidenced through photoborylation reactions and the generation of reactive oxygen species (ROS).
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Miniaturized spectrometers have emerged as pivotal tools in numerous scientific and industrial applications, offering advantages such as portability, cost-effectiveness, and the capability for onsite analysis. Despite these significant benefits, miniaturized spectrometers face critical challenges, particularly in sensitivity. Reduced dimensions often lead to compromises in optical path length and component quality, which can diminish detection limits and limit their applications in areas such as low-light-level measurements. Here we developed a compact spectrometer that integrates an array of photonic crystal slab filters with band-stop spectral transmission characteristics into an image sensor. Compared to traditional gratings or bandpass filter strategies, where each detector can only read light of a single wavelength component, our band-stop strategy allows each detector to read the light of all wavelengths except the band-stop wavelength. This maximizes energy extraction from incident signals, significantly improving the sensitivity of the spectrometer. Spectral reconstruction is achieved mathematically using pre-calibrated band-stop responses combined with a single coded image. Our spectrometer delivers a spectral resolution of 1.9â nm and demonstrates sensitivity more than ten times greater than that of conventional grating spectrometers during fluorescence spectroscopy of Ascaris lumbricoides. The design is fully compatible with complementary metal-oxide-semiconductor (CMOS) technology, allowing for mass production at low costs and thus promising broad deployment in sensitive applications.
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Nonreciprocity in acoustics is of paramount importance in many practical applications and has been experimentally realized using nonlinear media, moving fluids, or time modulation, which regrettably suffer from large volumes and high-power consumption, difficulty in integration, and inevitable vibrations or phase noise. In modern Hamiltonian theory, the violation of system's reciprocity can be achieved via asymmetric Peierls phases, which typically involves with non-Hermiticity or time-reversal symmetry breaking. Here, we propose a framework for designing nonreciprocal acoustic devices based on the asymmetric Peierls phases that can be fully controlled via active acoustic components. The fully controlled Peierls phases enable various high-performance acoustic devices, including non-Hermitian extensions of isolators, gyrators, and circulators, which are otherwise impossible in previous approaches that are bound by Hermiticity or passivity. We reveal that the transmission phases in isolators are equivalent to the Peierls phase plus a constant. The nonreciprocal phase delay in gyrators and the unirotational transmission behavior in circulators result from the gauge-invariant Aharonov-Bohm phases determined by Peierls phases. Our work not only uncovers multiple intriguing physics related to Peierls phases but also provides a general approach to compact, integratable, nonreciprocal acoustic devices.
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Quantum Hall systems host chiral edge states extending along the one-dimensional boundary of any two-dimensional sample. In solid state materials, the edge states serve as perfectly robust transport channels that produce a quantized Hall conductance; due to their chirality, and the topological protection by the Chern number of the bulk band structure, they cannot be spatially localized by defects or disorder. Here, we show experimentally that the chiral edge states of a lossy quantum Hall system can be localized. In a gyromagnetic photonic crystal exhibiting the quantum Hall topological phase, an appropriately structured loss configuration imparts the edge states' complex energy spectrum with a feature known as point-gap winding. This intrinsically non-Hermitian topological invariant is distinct from the Chern number invariant of the bulk (which remains intact) and induces mode localization via the "non-Hermitian skin effect." The interplay of the two topological phenomena-the Chern number and point-gap winding-gives rise to a non-Hermitian generalization of the paradigmatic Chern-type bulk-boundary correspondence principle. Compared to previous realizations of the non-Hermitian skin effect, the skin modes in this system have superior robustness against local defects and disorders.
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Photonic Chern insulators are known for their topological chiral edge states (CESs), whose absolute existence is determined by the bulk band topology, but concrete dispersion can be engineered to exhibit various properties. For example, the previous theory suggested that the edge dispersion can wind many times around the Brillouin zone to slow down light, which can potentially overcome fundamental limitations in conventional slow-light devices: narrow bandwidth and keen sensitivity to fabrication imperfection. Here, we report the first experimental demonstration of this idea, achieved by coupling CESs with resonance-induced nearly flat bands. We show that the backscattering-immune hybridized CESs are significantly slowed down over a relatively broad bandwidth. Our work thus paves an avenue to broadband topological slow-light devices.
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BACKGROUNDS: Mycoplasma pneumoniae (M. pneumoniae) is a common pathogen causing respiratory diseases in children. This study aimed to characterize epidemiological and disease severity shifts of M. pneumoniae: infections in Guangzhou, China during and after the coronavirus disease 2019 (COVID-19) pandemic. METHODS: Throat swab samples were obtained from 5405 hospitalized patients with symptoms of acute respiratory infections to detect M. pneumoniae. Differences in epidemiological and clinical characteristics of M. pneumoniae: infections were investigated during 2020-2022 and after COVID-19 pandemic (2023). RESULTS: M. pneumoniae were detected in 849 (15.6%, 849/5405) patients. The highest annual positive rate was 29.4% (754/2570) in 2023, followed by 5.3% (72/1367) in 2022, 1.2% (12/1015) in 2021, and 2.0% (11/553) in 2020, with significantly increasing annual prevalence from 2020 to 2023. M. pneumoniae incidence peaked between July and December post-COVID-19 pandemic in 2023, with the highest monthly positive rate (56.4%, 165/293). Clinical characteristics and outcomes of patients with M. pneumoniae did not vary between periods during and after COVID-19 pandemic except that patients with M. pneumoniae post-COVID-19 pandemic were more likely to develop fever. Patients with severe M. pneumoniae pneumonia (SMPP) were more likely to develop respiratory complications, myocardial damage, and gastrointestinal dysfunction than those with non-SMPP. Patients with SMPP had lower lymphocytes, CD3+ T cells, CD4+ T cells, CD8+ T cells, B cells, and higher IL-4, IL-6, IL-10 levels than those with non-SMPP. Bronchoalveolar lavage fluid specimens from infected patients were obtained to identify macrolide resistance mutations. Macrolide-resistant M. pneumoniae (MRMP) proportion in 2023 was 91.1% (215/236). CONCLUSION: Outbreaks of M. pneumoniae: occurred in Guangzhou, China in 2023 upon Non-pharmaceutical interventions easing. Despite the increasing incidence of M. pneumoniae, the disease severity remained similar during and after the COVID-19 pandemic.
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COVID-19 , Mycoplasma pneumoniae , Pneumonia por Mycoplasma , Humanos , China/epidemiologia , Pneumonia por Mycoplasma/epidemiologia , Pneumonia por Mycoplasma/microbiologia , COVID-19/epidemiologia , Mycoplasma pneumoniae/genética , Mycoplasma pneumoniae/isolamento & purificação , Masculino , Feminino , Criança , Adulto , Adolescente , Pessoa de Meia-Idade , Pré-Escolar , Adulto Jovem , Surtos de Doenças , SARS-CoV-2/genética , Lactente , Idoso , Incidência , Prevalência , PandemiasRESUMO
Unlike acoustic metasurfaces that rely solely on phase gradients, acoustic metagratings (AMs) operate based on both phase gradients and grating diffraction, thus further extending the generalized Snell's law (GSL). In particular, AMs can achieve reversal of refraction and reflection based on the parity of the number of wave propagations inside the AMs. So far, discussions of this GSL extension have largely been applied to one-dimensional periodic AMs, while the designs of two-dimensional (2D) periodic AMs and their performance in three-dimensional (3D) space have been quite limited. Here, we study the GSL extension in 3D space and experimentally demonstrate a series of functional 2D periodic AMs. The designed AMs can achieve sound refraction/reflection under any incidence angle in 3D space, without restrictions to certain critical ranges; adjusting incident angles only enables the reversal of refraction and reflection. Additionally, we demonstrate two types of dual-layer sound lenses based on two AMs, whose reversal of refraction and reflection can be realized by simply attaching or separating the two AMs. Our work paves the way to complex 3D wavefront manipulation of AMs, which may find potential use in practical acoustic devices.
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The loss of midbrain dopaminergic (DA) neurons is the fundamental pathological feature of Parkinson's disease (PD). PD causes chronic pain in two-thirds of patients. Recent studies showed that the activation of the pedunculopontine tegmental nucleus (PPTg) can effectively relieve inflammatory pain and neuropathic pain. The PPTg is located in the pontomesencephalic tegmentum, a target of deep brain stimulation (DBS) treatment in PD, and is involved in motor control and sensory integration. To test whether the lesion of midbrain DA neurons induced pain hypersensitivity, and whether the chemogenetic activation of the PPTg could modulate the pain, the AAV-hM3Dq receptor was transfected and expressed into the PPTg neurons of 6-hydroxydopamine-lesioned mice. In this study, von Frey, open field, and adhesive tape removal tests were used to assess animals' pain sensitivity, locomotor activity, and sensorimotor function and somatosensory perception, respectively. Here, we found that the lesion of midbrain DA neurons induced a minor deficit in voluntary movement but did not affect sensorimotor function and somatosensory perception in the tape removal test. The results showed that lesion led to pain hypersensitivity, which could be alleviated both by levodopa and by the chemogenetic activation of the PPTg. Activating the PPTg may be a potential therapeutic strategy to relieve pain phenotypes in PD.
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Neurônios Dopaminérgicos , Mesencéfalo , Núcleo Tegmental Pedunculopontino , Animais , Núcleo Tegmental Pedunculopontino/metabolismo , Neurônios Dopaminérgicos/metabolismo , Camundongos , Mesencéfalo/metabolismo , Masculino , Doença de Parkinson/terapia , Doença de Parkinson/fisiopatologia , Dor/etiologia , Dor/metabolismo , Camundongos Endogâmicos C57BL , Estimulação Encefálica Profunda/métodos , Modelos Animais de Doenças , Levodopa/farmacologia , OxidopaminaRESUMO
The synthesis of single-crystalline and robust pyrazolate metal-organic frameworks (Pz-MOFs) capable of facilitating challenging organic transformations is fundamentally significant in catalysis. Here we demonstrate a metal-node-based catalytic site anchoring strategy by synthesizing a single-crystalline and robust Pz-MOF (PCN-1004). PCN-1004 features one-dimensional (1D) copper-Pz chains interconnected by well-organized ligands, forming a porous three-dimensional (3D) network with two types of 1D open channels. Notably, PCN-1004 displays exceptional stability in aqueous solutions across a broad pH range (1 to 14), attributed to the robust copper-Pz coordination bonds. Significantly, PCN-1004 functions as an outstanding catalyst in cross dehydrogenative coupling reactions for constructing C-O/C-S bonds, even in the absence of directing groups, achieving yields of up to ~99%, with long cycle lives and high substrate compatibility. PCN-1004 outperforms all previously reported porphyrin-based homogeneous and heterogeneous catalysts. Control experiments and computations elucidate the pivotal catalytic role of the copper-Pz chains and reveal a free radical pathway for the reaction. This work not only demonstrates the successful implementation of a metal-node-based catalytic site anchoring strategy for the efficient catalysis of challenging organic transformations but also highlights the synergistic effect of a robust framework, 1D open channels, and active sites in enhancing catalytic efficiency within MOFs.
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For the classification of topological phases of matter, an important consideration is whether a system is spinless or spinful, as these two classes have distinct symmetry algebra that gives rise to fundamentally different topological phases. However, only recently has it been realized theoretically that in the presence of gauge symmetry, the algebraic structure of symmetries can be projectively represented, which possibly enables the switch between spinless and spinful topological phases. Here, we report the experimental demonstration of this idea by realizing spinful topological phases in "spinless" acoustic crystals with projective space-time inversion symmetry. In particular, we realize a one-dimensional topologically gapped phase characterized by a 2Z winding number, which features double-degenerate bands in the entire Brillouin zone and two pairs of degenerate topological boundary modes. Our Letter thus overcomes a fundamental constraint on topological phases by spin classes.