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Short peptides are attractive building blocks for the fabrication of self-assembled materials with significant biological, chemical, and physical properties. The microscopic and macroscopic properties of assemblies are usually closely related to the dimensionality of formed hydrogen bond networks. Here, two completely different supramolecular architectures connected by distinct hydrogen bond networks were obtained by simply adding a hydroxyl group to switch from cyclo-tryptophan-alanine (cyclo-WA) to cyclo-tryptophan-serine (cyclo-WS). While hydroxyl-bearing cyclo-WS molecules provided an additional hydrogen bond donor that links to adjacent molecules, forming a rigid three-dimensional network, cyclo-WA arranged into a water-mediated zipper-like structure with a softer two-dimensional layer template. This subtle alteration resulted in a 14-fold enhancement of Young's modulus values in cyclo-WS compared to cyclo-WA. Both cyclo-dipeptides exhibit biocompatibility, high fluorescence, and piezoelectricity. The demonstrated role of dimensionality of hydrogen bond networks opens new avenues for rational design of materials with precise morphologies and customizable properties for bioelectronic applications.
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Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193 nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS-), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS-), and triflate (TF-), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS+), particularly at â¼193 nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. We observed the lowest vertical detachment energy of 6.6 eV of pTS- in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193 nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS-, 308.1 kcal/mol for TFMBS-, and 303.2 kcal/mol for TF-, which suggest the increasing acidity strength, yet even the weakest acid pTS- is still stronger than strong acid HBr. The photolysis of TPS+-based PAG, TPS+·pTS-, generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS- displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.
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BACKGROUND: Antarctic krill peptide (AKP) has gained considerable interest because of its multiple biological functions. However, its application may be limited by its poor stability and susceptibility to degradation. Encapsulation of AKP using a nanoparticle delivery system is an effective way to overcome these problems. In the present study, bovine serum albumin (BSA) and chitosan (CS) were used as delivery vehicles to encapsulate AKP. RESULTS: The results revealed that the particle size (83.3 ± 4.4-222.4 ± 32.7 nm) and zeta-potential (35.1 ± 0.7-45.0 ± 2.7 mV) of nanoparticles (NPs) increased with the increasing content of BSA, but the polydispersity index decreased (1.000 ± 0.002 to 0.306 ± 0.011). Hydrogen bonding, hydrophobic and electrostatic interactions were the main forces to form BSA/CS-AKP NPs. X-ray diffraction revealed that AKP was encapsulated by BSA/CS. Scanning electron microscopy images exhibited that the NPs were spherical in shape, uniform in size and tightly bound. BSA/CS-AKP NPs exhibited excellent stability in the pH range (2-5) and after 15 days of storage, and could hinder the release of AKP in simulated gastric environment and promote the release of AKP in simulated intestinal environment. After simulated digestion, the hypoglycemic activity of encapsulated AKP was better than that of unencapsulated AKP. CONCLUSION: Our results revealed that the BSA/CS showed great potential for protecting and delivering AKP. © 2024 Society of Chemical Industry.
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Lower extremity nodular melanoma (NM) is a common malignant tumor with a poor prognosis. We aims to identify the prognostic factors and develop a nomogram model to predict overall survival (OS) in patients with lower extremity NM. A total of 746 patients with lower extremity NM were selected and randomly divided into a training set (522 cases) and a validation set (224 cases) from the Surveillance, Epidemiology, and End Results(SEER) database. The training set underwent univariate and multivariate Cox regression analyses to identify independent prognostic factors associated with patient outcomes, and to develop a nomogram model. The effectiveness of the nomogram was subsequently validated using the validation set. Multivariable Cox regression analysis of the training set indicated that age, ulceration, radiotherapy, chemotherapy, primary site of first malignant tumor, and Breslow thickness were independent variables associated with OS. In the training set, the area under the curve (AUC) of the nomogram for predicting 3-year and 5-year OS was 0.796 and 0.811, respectively. In the validation set, the AUC for predicting 3-year and 5-year OS was 0.694 and 0.702, respectively. The Harrell's C-index for the training set and validation set were 0.754 (95% CI: 0.721-0.787) and 0.670 (95% CI: 0.607-0.733), respectively. Calibration curves for both training and validation sets showed good agreement. In this study, we develop and validate a nomogram to predict OS in patients with lower extremity NM. The nomogram demonstrated reasonable reliability and clinical applicability. Nomograms are important tools assessing prognosis and aiding clinical decision-making.
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Extremidad Inferior , Melanoma , Nomogramas , Programa de VERF , Neoplasias Cutáneas , Humanos , Melanoma/mortalidad , Melanoma/diagnóstico , Melanoma/patología , Melanoma/terapia , Melanoma/epidemiología , Masculino , Femenino , Programa de VERF/estadística & datos numéricos , Persona de Mediana Edad , Pronóstico , Neoplasias Cutáneas/mortalidad , Neoplasias Cutáneas/patología , Neoplasias Cutáneas/diagnóstico , Neoplasias Cutáneas/terapia , Anciano , Adulto , Anciano de 80 o más AñosRESUMEN
Microhydrated closo-boranes have attracted great interest due to their superchaotropic activity related to the well-known Hofmeister effect and important applications in biomedical and battery fields. In this work, we report a combined negative ion photoelectron spectroscopy and quantum chemical investigation on hydrated closo-decaborate clusters [B10H10]2-·nH2O (n = 1-7) with a direct comparison to their analogues [B12H12]2-·nH2O and free water clusters. A single H2O molecule is found to be sufficient to stabilize the intrinsically unstable [B10H10]2- dianion. The first two water molecules strongly interact with the solute forming B-H···H-O dihydrogen bonds while additional water molecules show substantially reduced binding energies. Unlike [B12H12]2-·nH2O possessing a highly structured water network with the attached H2O molecules arranged in a unified pattern by maximizing B-H···H-O dihydrogen bonding, distinct structural arrangements of the water clusters within [B10H10]2-·nH2O are achieved with the water cluster networks from trimer to heptamer resembling free water clusters. Such a distinct difference arises from the variations in size, symmetry, and charge distributions between these two dianions. The present finding again confirms the structural diversity of hydrogen-bonding networks in microhydrated closo-boranes and enriches our understanding of aqueous borate chemistry.
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BACKGROUND: The widespread use of quercetin is limited by its instability, low solubility and poor oral bioavailability. Encapsulation of quercetin using a nanoparticle delivery system is an effective way to overcome these drawbacks. RESULTS: The effect of the molecular weight (Mw) of chitosan (CS) (100, 200, 500 and 1000 kDa) on quercetin-loaded chitosan nanoparticles (QCNPs) was investigated. The structure, stability, release properties and antioxidant activities of the nanoparticles (QCNP-10, QCNP-20, QCNP-50 and QCNP-100) were assessed. Particle size of QCNPs decreased and polydispersity index increased with the increasing Mw of CS. The main forces involved in the formation of QCNPs were hydrogen bonding and hydrophobic interaction. X-ray diffraction verified that quercetin was loaded into CS nanoparticles. The photostability and thermal stability of QCNPs increased with increasing Mw of CS. QCNP-100 exhibited the lowest release rate in a mixture of water and anhydrous ethanol. The antioxidant activities of QCNPs were enhanced with increasing Mw of CS, and QCNP-100 possessed the highest antioxidant activities, which might be relevant to its smallest particle size. CONCLUSION: Overall, these results revealed that the Mw of CS affected the properties of QCNPs, and QCNP-100 possessed the smallest particle, best stability, lowest release rate and highest antioxidant activities. © 2024 Society of Chemical Industry.
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The oxidation of phenolic compounds is one of the most important reactions prevalent in various biological processes, often explicitly coupled with proton transfers (PTs). Quantitative descriptions and molecular-level understanding of these proton-coupled electron transfer (PCET) reactions have been challenging. This work reports a direct observation of PCET in photodetachment (PD) photoelectron spectroscopy (PES) of hydrogen-bonded phenolic (ArOH) nitrate (NO3-) complexes, in which a much slower rising edge provides a spectroscopic signature to evidence PCET. Electronic structure calculations unveil the PCET processes to be isomer-specific, occurred only in those with their HOMOs localized on ArOH, leading to charge-separated transient states ArOHâ¢+·NO3- triggered by ionizing phenols while simultaneously promoting PT from ArOHâ¢+ to NO3-. Importantly, this study showcases that gas-phase PD-PES is a generic means enabling to identify PCET reactions with explicit structural and binding information.
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Neurological disorders exert significantly affect the quality of life for patients, necessitating effective strategies for nerve regeneration. Both traditional autologous nerve transplantation and emerging therapeutic approaches encounter scientific challenges due to the complex nature of the nervous system and the unsuitability of the surrounding environment for cell transplantation. Tissue engineering techniques offer a promising path for neurotherapy. Successful neural tissue engineering relies on modulating cell differentiation behavior and tissue repair by developing biomaterials that mimic the natural extracellular matrix (ECM) and establish a three-dimensional microenvironment. Peptide-based hydrogels have emerged as a potent option among these biomaterials due to their ability to replicate the structure and complexity of the ECM. This review aims to explore the diverse range of peptide-based hydrogels used in nerve regeneration with a specific focus on dipeptide hydrogels, tripeptide hydrogels, oligopeptide hydrogels, multidomain peptides (MDPs), and amphiphilic peptide hydrogels (PAs). Peptide-based hydrogels offer numerous advantages, including biocompatibility, structural diversity, adjustable mechanical properties, and degradation without adverse effects. Notably, hydrogels formed from self-assembled polypeptide nanofibers, derived from amino acids, show promising potential in engineering neural tissues, outperforming conventional materials like alginate, poly(ε-caprolactone), and polyaniline. Additionally, the simple design and cost-effectiveness of dipeptide-based hydrogels have enabled the creation of various functional supramolecular structures, with significant implications for nervous system regeneration. These hydrogels are expected to play a crucial role in future neural tissue engineering research. This review aims to highlight the benefits and potential applications of peptide-based hydrogels, contributing to the advancement of neural tissue engineering.
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Mesenchymal stem cells (MSCs) are essential in regenerative medicine. However, conventional expansion and harvesting methods often fail to maintain the essential extracellular matrix (ECM) components, which are crucial for their functionality and efficacy in therapeutic applications. Here, we introduce a bone marrow-inspired macroporous hydrogel designed for the large-scale production of MSC-ECM spheroids. Through a soft-templating approach leveraging liquid-liquid phase separation, we engineer macroporous hydrogels with customizable features, including pore size, stiffness, bioactive ligand distribution, and enzyme-responsive degradability. These tailored environments are conducive to optimal MSC proliferation and ease of harvesting. We find that soft hydrogels enhance mechanotransduction in MSCs, establishing a standard for hydrogel-based 3D cell culture. Within these hydrogels, MSCs exist as both cohesive spheroids, preserving their innate vitality, and as migrating entities that actively secrete functional ECM proteins. Additionally, we also introduce a gentle, enzymatic harvesting method that breaks down the hydrogels, allowing MSCs and secreted ECM to naturally form MSC-ECM spheroids. These spheroids display heightened stemness and differentiation capacity, mirroring the benefits of a native ECM milieu. Our research underscores the significance of sophisticated materials design in nurturing distinct MSC subpopulations, facilitating the generation of MSC-ECM spheroids with enhanced therapeutic potential.
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Matriz Extracelular , Hidrogeles , Células Madre Mesenquimatosas , Esferoides Celulares , Células Madre Mesenquimatosas/citología , Células Madre Mesenquimatosas/metabolismo , Hidrogeles/química , Matriz Extracelular/metabolismo , Esferoides Celulares/citología , Esferoides Celulares/metabolismo , Humanos , Diferenciación Celular , Técnicas de Cultivo de Célula/métodos , Proliferación Celular , Porosidad , Mecanotransducción Celular/fisiología , Células CultivadasRESUMEN
A series of anionic transition metal halides, OsCln- (n = 3-5), have been investigated using a newly developed, home-constructed, cryogenic anion cluster photoelectron spectroscopy. The target anionic species are generated through collision-induced dissociation in a two-stage ion funnel. The measured vertical detachment energies (VDEs) are 3.48, 4.54, and 4.81 eV for n = 3, 4, and 5, respectively. Density functional theory calculations at the B3LYP-D3(BJ)//aug-cc-pVTZ(-pp) level predict the lowest energy structures of the atomic form of OsCln- (n = 3-5) to be a quintet triangle, quartet square, and quintet square-based pyramid, respectively. The CCSD(T)-calculated VDEs and corresponding adiabatic detachment energies agree well with our experimental measurements. Analysis of the corresponding frontier molecular orbitals and charge density differences suggests that the d-orbitals of the transition metal Os play a primary role in the single-photon detachment processes, and the detached electrons originating from different molecular orbitals are distinguishable.
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Pentachlorophenol (PCP) was once used as a pesticide, germicide, and preservative due to its stable properties and resistance to degradation. This study aimed to design a biosensor for the quantitative and prompt detection of capable of PCP. A cell-free fluorescence biosensor was developed while employing NalC, an allosteric Transcription Factor responsive to PCP and In Vitro Transcription. By adding a DNA template and PCP and employing Electrophoretic Mobility Shift Assay while monitoring the dynamic fluorescence changes in RNA, this study offers evidence of NalC's potential applicability in sensor systems developed for the specific detection of PCP. The biosensor showed the capability for the quantitative detection of PCP, with a Limit of Detection (LOD) of 0.21 µM. Following the addition of Nucleic Acid Sequence-Based Amplification, the fluorescence intensity of RNA revealed an excellent linear relationship with the concentration of PCP, showing a correlation coefficient (R2) of 0.9595. The final LOD was determined to be 0.002 µM. This study has successfully translated the determination of PCP into a fluorescent RNA output, thereby presenting a novel approach for detecting PCP within environmental settings.
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Hydrogels capable of swift mechanical energy dissipation hold promise for a range of applications including impact protection, shock absorption, and enhanced damage resistance. Traditional energy absorption in such materials typically relies on viscoelastic mechanisms, involving sacrificial bond breakage, yet often suffers from prolonged recovery times. Here, we introduce a hydrogel designed for friction-based damping. This hydrogel features an internal structure that facilitates the motion of a chain walker within its network, effectively dissipating mechanical stress. The hydrogel network architecture allows for rapid restoration of its damping capacity, often within seconds, ensuring swift material recovery post-deformation. We further demonstrate that this hydrogel can significantly shield encapsulated cells from mechanical trauma under repetitive compression, owing to its proficient energy damping and rapid rebound characteristics. Therefore, this hydrogel has potential for dynamic load applications like artificial muscles and synthetic cartilage, expanding the use of hydrogel dampers in biomechanics and related areas.
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Similarity-based prediction methods utilize degradation trend analysis based on degradation indicators (DIs). These methods are gaining prominence in industrial predictive maintenance because they effectively address prognostics for machines with unknown failure mechanisms. However, current studies often neglect the discrepancies in degradation trends when constructing DIs from multi-sensor data and lack automatic normalization of operating regimes during feature fusion. In this study, a feature fusion methodology based on a signal-to-noise ratio metric that leverages slow feature analysis (SFA) is proposed. This customized metric utilizes SFA to quantify degradation trend discrepancies of constructed DIs, while automatically filtering out the effects of multiple operating regimes during feature fusion. The effectiveness and superiority of the proposed method are demonstrated using publicly available aero-engine and rolling bearing datasets.
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Heat-activated second harmonic generation (SHG) switching materials are gaining interest for their ability to switch between SHG on and off states, offering potential in optoelectronic applications. The novel nonlinear optical (NLO) switch, (C5H6NO)+(CH3SO3)- (4-hydroxypyridinium methylsulfonate, 4HPMS), is a near-room-temperature thermal driven material with a strong SHG response (3.3 × KDP), making it one of the most potent heat-stimulated NLO switches. It offers excellent contrast of 13 and a high laser-induced damage threshold (2.5 × KDP), with reversibility > 5â cycles. At 73 °C, 4HPMS transitions from the noncentrosymmetric Pna21 room temperature phase (RTP) to the centrosymmetric P21/c phase, caused by the rotation of the (C5H6NO)+ and (CH3SO3)- due to partially thermal breaking of intermolecular hydrogen bonds. The reverse phase change exhibits a large 50 °C thermal hysteresis. Density functional theory (DFT) calculations show that (C5H6NO)+ primarily dictates both the SHG coefficient (dij) and birefringence (âµn(Zeiss) = 0.216 vs âµn(cal.) = 0.202 at 546â nm; Δn(Immersion) = 0.210 vs âµn(cal.) = 0.198 at 589.3â nm), while the band gap (Eg) is influenced synergistically by (C5H6NO)+ and (CH3SO3)-. Additionally, 4HPMS-RTP also exhibits mechanochromism upon grinding as well as an aggregation-enhanced emission in a mixture of acetone and water.
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Recent research on mechano-radicals has provided valuable insights into self-growth and adaptive responsive materials. Typically, mechanophores must remain inert in the absence of force but respond quickly to external tension before other linkages within the polymer network. Azo compounds exhibit promising combinations of mechanical stability and force-triggered reactivity, making them widely used as mechano-radicals in force-responsive materials. However, the activation conditions and behavior of azo compounds have yet to be quantitatively explored. In this study, we investigated the mechanical strength of three azo compounds using single-molecule force spectroscopy. Our results revealed that these compounds exhibit rupture forces ranging from ~500 to 1000â pN, at a loading rate of 3×104â pN s-1. Importantly, these mechanophores demonstrate distinct kinetic properties. Their unique mechanical attributes enable azo bond scission and free radical generation before causing major polymer backbone damage of entire material during polymer network deformation. This fundamental understanding of mechanophores holds significant promise for the development of self-growth materials and their related applications.
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Pathogenic bacterial infections, even at extremely low concentrations, pose significant threats to human health. However, the challenge persists in achieving high-sensitivity bacterial detection, particularly in complex samples. Herein, we present a novel sandwich-type electrochemical sensor utilizing bacteria-imprinted polymer (BIP) coupled with vancomycin-conjugated MnO2 nanozyme (Van@BSA-MnO2) for the ultrasensitive detection of pathogenic bacteria, exemplified by Staphylococcus aureus (S. aureus). The BIP, in situ prepared on the electrode surface, acts as a highly specific capture probe by replicating the surface features of S. aureus. Vancomycin (Van), known for its affinity to bacterial cell walls, is conjugated with a Bovine serum albumin (BSA)-templated MnO2 nanozyme through EDC/NHS chemistry. The resulting Van@BSA-MnO2 complex, serving as a detection probe, provides an efficient catalytic platform for signal amplification. Upon binding with the captured S. aureus, the Van@BSA-MnO2 complex catalyzes a substrate reaction, generating a current signal proportional to the target bacterial concentration. The sensor displays remarkable sensitivity, capable of detecting a single bacterial cell in a phosphate buffer solution. Even in complex milk matrices, it maintains outstanding performance, identifying S. aureus at concentrations as low as 10 CFU mL-1 without requiring intricate sample pretreatment. Moreover, the sensor demonstrates excellent selectivity, particularly in distinguishing target S. aureus from interfering bacteria of the same genus at concentrations 100-fold higher. This innovative method, employing entirely synthetic materials, provides a versatile and low-cost detection platform for Gram-positive bacteria. In comparison to existing nanozyme-based bacterial sensors with biological recognition materials, our assay offers distinct advantages, including enhanced sensitivity, ease of preparation, and cost-effectiveness, thereby holding significant promise for applications in food safety and environmental monitoring.
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Compuestos de Manganeso , Óxidos , Polímeros , Staphylococcus aureus , Vancomicina , Staphylococcus aureus/aislamiento & purificación , Compuestos de Manganeso/química , Óxidos/química , Vancomicina/química , Polímeros/química , Albúmina Sérica Bovina/química , Técnicas Electroquímicas/métodos , Análisis de la Célula Individual , Antibacterianos/química , Antibacterianos/farmacología , Animales , Límite de Detección , Polímeros Impresos Molecularmente/química , HumanosRESUMEN
Gambogic acid is a natural compound with anticancer properties and is effective for many tumors. But its low water solubility and dose-dependent side effects limit its clinical application. This study aims to develop a novel drug delivery system for intratumoral delivery of gambogic acid. In our experimental study, we propose a new method for encapsulating gambogic acid nanoparticles using a manganese composite hyaluronic acid hydrogel as a carrier, designed for targeted drug delivery to tumors. The hydrogel delivery system is synthesized through the coordination of hyaluronic acid-dopamine (HA-DOPA) and manganese ions. The incorporation of manganese ions serves three purposes:1.To form cross-linked hydrogels, thereby improving the mechanical properties of HA-DOPA.2.To monitor the retention of hydrogels in vivo in real-time using magnetic resonance imaging (MRI).3.To activate the body's immune response. The experimental results show that the designed hydrogel has good biosafety, in vivo sustained release effect and imaging tracking ability. In the mouse CT26 model, the hydrogel drug-loaded group can better inhibit tumor growth. Further immunological analysis shows that the drug-loaded hydrogel group can stimulate the body's immune response, thereby better achieving anti-tumor effects. These findings indicate the potential of the developed manganese composite hyaluronic acid hydrogel as an effective and safe platform for intratumoral drug delivery. The amalgamation of biocompatibility, controlled drug release, and imaging prowess positions this system as a promising candidate for tumor treatment.
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Ácido Hialurónico , Hidrogeles , Manganeso , Nanopartículas , Xantonas , Ácido Hialurónico/química , Animales , Manganeso/química , Xantonas/química , Xantonas/farmacología , Xantonas/administración & dosificación , Ratones , Nanopartículas/química , Hidrogeles/química , Portadores de Fármacos/química , Sistemas de Liberación de Medicamentos , Línea Celular Tumoral , Liberación de Fármacos , Humanos , Antineoplásicos/química , Antineoplásicos/farmacología , Antineoplásicos/administración & dosificación , Imagen por Resonancia MagnéticaRESUMEN
Intravenous thrombolysis with recombinant tissue plasminogen activator (rtPA) is the primary treatment for ischemic stroke. However, rtPA treatment can substantially increase blood-brain barrier (BBB) permeability and susceptibility to hemorrhagic transformation. Herein, the mechanism underlying the side effects of rtPA treatment is investigated and demonstrated that ferroptosis plays an important role. The ferroptosis inhibitor, liproxstatin-1 (Lip) is proposed to alleviate the side effects. A well-designed macrocyclic carrier, glucose-modified azocalix[4]arene (GluAC4A), is prepared to deliver Lip to the ischemic site. GluAC4A bound tightly to Lip and markedly improved its solubility. Glucose, modified at the upper rim of GluAC4A, imparts BBB targeting to the drug delivery system owing to the presence of glucose transporter 1 on the BBB surface. The responsiveness of GluAC4A to hypoxia due to the presence of azo groups enabled the targeted release of Lip at the ischemic site. GluAC4A successfully improved drug accumulation in the brain, and Lip@GluAC4A significantly reduced ferroptosis, BBB leakage, and neurological deficits induced by rtPA in vivo. These findings deepen the understanding of the side effects of rtPA treatment and provide a novel strategy for their effective mitigation, which is of great significance for the treatment and prognosis of patients with ischemic stroke.
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Modelos Animales de Enfermedad , Sistemas de Liberación de Medicamentos , Ferroptosis , Accidente Cerebrovascular Isquémico , Activador de Tejido Plasminógeno , Animales , Ferroptosis/efectos de los fármacos , Ratones , Accidente Cerebrovascular Isquémico/tratamiento farmacológico , Activador de Tejido Plasminógeno/farmacología , Activador de Tejido Plasminógeno/administración & dosificación , Sistemas de Liberación de Medicamentos/métodos , Barrera Hematoencefálica/efectos de los fármacos , Barrera Hematoencefálica/metabolismo , Masculino , Quinoxalinas , Compuestos de EspiroRESUMEN
Cylindrospermopsin (CYN), a cyanobacterial toxin, has been detected in the global water environment. However, information concerning the potential environmental risk of CYN is limited, since the majority of previous studies have mainly focused on the adverse health effects of CYN through contaminated drinking water. The present study reported that CYN at environmentally relevant levels (0.1-100⯵g/L) can significantly enhance the conjugative transfer of RP4 plasmid in Escherichia coli genera, wherein application of 10⯵g/L of CYN led to maximum fold change of â¼6.5- fold at 16â¯h of exposure. Meanwhile, evaluation of underlying mechanisms revealed that environmental concentration of CYN exposure could increase oxidative stress in the bacterial cells, resulting in ROS overproduction. In turn, this led to an upregulation of antioxidant enzyme-related genes to avoid ROS attack. Further, inhibition of the synthesis of glutathione (GSH) was also detected, which led to the rapid depletion of GSH in cells and thus triggered the SOS response and promoted the conjugative transfer process. Increase in cell membrane permeability, upregulation of expression of genes related to pilus generation, ATP synthesis, and RP4 gene expression were also observed. These results highlight the potential impact on the spread of antimicrobial resistance in water environments.
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Alcaloides , Toxinas Bacterianas , Toxinas de Cianobacterias , Escherichia coli , Glutatión , Plásmidos , Uracilo , Plásmidos/genética , Glutatión/metabolismo , Escherichia coli/efectos de los fármacos , Escherichia coli/genética , Toxinas Bacterianas/toxicidad , Uracilo/análogos & derivados , Uracilo/toxicidad , Estrés Oxidativo/efectos de los fármacos , Especies Reactivas de Oxígeno/metabolismo , Conjugación Genética , Farmacorresistencia Bacteriana Múltiple/efectos de los fármacos , Farmacorresistencia Bacteriana Múltiple/genéticaRESUMEN
Despite being an important closo-borate in condensed phase boron chemistry, isolated [B10H10]2- is electronically unstable and has never been detected in the gas phase. Herein, we report a successful capture of this fleeting species through binding with an octamethylcalix[4]pyrrole (omC4P) molecule to form a stable gaseous omC4P·[B10H10]2- complex and its characterizations utilizing negative ion photoelectron spectroscopy (NIPES). The recorded NIPE spectrum, contributed by both omC4P and [B10H10]2-, is deconvoluted by subtracting the omC4P contribution to yield a [B10H10]2- spectrum. The obtained [B10H10]2- spectrum consists of four major bands spanning the electron binding energy (EBE) range from 1 to 5 eV, with the EBE gaps matching excellently with the energy intervals of computed high-lying occupied molecular orbitals of the [B10H10]2- dianion. This study showcases a generic method to utilize omC4P to capture unstable multiply charged anions in the gas phase for experimental determination of their electronic structures.