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The separation of BTEX [benzene, toluene, ethylbenzene (EB), and xylene isomers] poses a huge challenge in the industry, attributed to their similar structures and physical properties. Supramolecular compounds show great promise for hydrocarbon separation. Herein, we designed two pairs of endo-functionalized amide naphthotubes with methyl and benzyl side chains, which were first employed as chromatographic separation materials and exhibited high shape-selectivity for BTEX. In particular, the amide naphthotubes with methyl side chains provided complete separation toward BTEX and anti-3a showed high selectivity for the p-xylene over other isomers with αPX/OX = 9.34, αPX/MX = 5.50, and αPX/EB = 4.30. The mechanism of BTEX separation originates from the synergistic effect of specially confined tandem N-H···π and C-H···π interactions toward aromatic compounds. The findings of this research show promise for practical applications in efficiently separating crucial aromatic isomers.
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Patients with systemic lupus erythematosus (SLE), a heterogeneous and chronic autoimmune disease, exhibit unique changes in the complex composition and transcriptional signatures of peripheral blood mononuclear cells (PBMCs). While the mechanism of pathogenesis for both childhood-onset SLE (cSLE) and adult-onset SLE (aSLE) remains unclear, cSLE patients are considered more unpredictable and dangerous than aSLE patients. In this study, we analysed single-cell RNA sequencing data (scRNA-seq) to profile the PBMC clusters of cSLE/aSLE patients and matched healthy donors and compared the PBMC composition and transcriptional variations between the two groups. Our analysis revealed that the PBMC composition and transcriptional variations in cSLE patients were similar to those in aSLE patients. Comparative single-cell transcriptome analysis between healthy donors and SLE patients revealed IFITM3, ISG15, IFI16 and LY6E as potential therapeutic targets for both aSLE and cSLE patients. Additionally, we observed that the percentage of pre-B cells (CD34-) was increased in cSLE patients, while the percentage of neutrophil cells was upregulated in aSLE patients. Notably, we found decreased expression of TPM2 in cSLE patients, and similarly, TMEM150B, IQSEC2, CHN2, LRP8 and USP46 were significantly downregulated in neutrophil cells from aSLE patients. Overall, our study highlights the differences in complex PBMC composition and transcriptional profiles between cSLE and aSLE patients, providing potential biomarkers that could aid in diagnosing SLE.
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Leucócitos Mononucleares , Lúpus Eritematoso Sistêmico , Adulto , Humanos , Criança , Idade de Início , Lúpus Eritematoso Sistêmico/diagnóstico , Lúpus Eritematoso Sistêmico/genética , Lúpus Eritematoso Sistêmico/tratamento farmacológico , Índice de Gravidade de Doença , Análise de Célula Única , Proteínas de Membrana , Proteínas de Ligação a RNA , Fatores de Troca do Nucleotídeo GuaninaRESUMO
Enantioselective recognition of functional organic molecules in water is routine in nature but remains a formidable challenge for synthetic hosts. Here, we reported two pairs of chiral naphthotubes with chiral centers located in the neighborhood of the inward-directing amide groups. These naphthotubes, with a chiral twisted cavity, show highly enantioselective recognition in water to a wide scope of organic molecules (90 chiral guests). The highest enantioselectivity of 34 was achieved with neotame. Small differences between all of the noncovalent interactions shielded in the hydrophobic cavity were revealed to be responsible for the enantioselective recognition in water, which is different from the traditional views. Moreover, these hosts can differentiate the analogues of aspartame using fluorescence spectroscopy. These chiral naphthotubes have made unprecedented achievements in enantioselective recognition, providing the basis for their applications in chiral analysis and separations.
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Many strategies have been developed for constructing anisotropic hydrogels, however, it remains a challenge to fabricate hydrogels with anisotropic nanocrystalline domains from intrinsically soft networks. Here, we report a naphthotube-based polyrotaxane-containing hydrogel that can be reinforced via mechanical training. During the training process, the hydrogel can adopt reorientation of polymer chains to form anisotropic structures driven by external uniaxial force. Due to the multiple hydrogen bonding sites and movable feature of naphthotube, the sliding of naphthotube on PEG chains simultaneously inducing the zipping of adjacent polymer chains to form densely anisotropic nanocrystalline domains through hydrogen bonded networks. Thus, the trained hydrogel exhibits an enhanced tension stress of ≈110â kPa, which realize a remarkable enhancement of ≈10â times compare to initial state. This study provides a new tactic for improving the mechanical performance of soft materials.
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Since the implementation of the IP strategy in 2008, It has been agreed that intellectual property rights can promote regional economic development, but how to promote it is a black box. Based on the theory of system dynamics, three systems have been divided from the promoting effect of intellectual property on regional economy: intellectual property management system, technology innovation dynamic system and government policy support dynamic system. By analyzing the driving relationship among the three systems, It is found that intellectual property can promote regional economic growth through technological innovation. The government's policy support and the implementation of intellectual property strategy promote the innovation motivation of enterprises under the action of market mechanism. In the final analysis, enterprises are the main force of economic growth. They can improve the level of technological innovation through industry-university-research cooperation and other ways to obtain innovation benefits, so as to promote regional economic growth.
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Desenvolvimento Econômico , Propriedade Intelectual , China , Humanos , Indústrias , Invenções , UniversidadesRESUMO
Soil respiration, particularly heterotrophic respiration (RH), is a potent source of carbon dioxide (CO2) in the atmosphere. The current research focuses on the evaluation of RH for six land use systems including sloping cropland (SC), shrub land (SD), grassland (GD), shrub & grassland (SGD), newly abandoned cropland (NC) and afforested forest (AF). Heterotrophic respiration showed a diverse seasonal pattern over a year long period that was affected by various soil properties and climatic variables across the six land use systems in a subtropical Karst landscape. The lowest RH scores were found in the SD site (annual cumulative soil CO2 flux: 2447 kg C ha-1), whereas the maximum heterotrophic respiration occurred in the SF site (annual cumulative soil CO2 13597 kg C ha-1). The values of RH were: SC site: 3.8-191.5 mg C m-2 h-1, NC site: 1.04-129 mg C m-2 h-1, GD site: 3.6-100.7 mg C m-2 h-1, SGD site: 0.3-393.5 mg C m-2 h-1, SD site: 3-116 mg C m-2 h-1, and SF site: 10.6-398.2 mg C m-2 h-1. Highly significant (p ≤ 0.01) and positive correlations between RH rate and soil temperature were found for the studied land use types (correlation coefficients as follows; SC: 0.77, NC: 0.61, GD: 0.283, SGD: 0.535, SD: 0.230, SF: 0.85). However, water filled pore space (WFPS), NH4+, NO3-, dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) concentrations showed varied (positive and negative) correlations with RH. The overall results show that soil temperature can be considered as the most limiting factor for RH among all the sites studied in the present research. In these environments, soil heterotrophic respiration significantly correlated with soil temperature, highlighting the significance of climate on heterotrophic respiration.
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Dióxido de Carbono , Solo , Dióxido de Carbono/análise , China , Florestas , Respiração , TemperaturaRESUMO
RATIONALE: Alport syndrome (AS) is an inherited progressive renal failure, characterized by kidney disease, hearing loss, and eye abnormalities. PATIENT CONCERNS: A 7-year-old male child was admitted for persistent microscopic hematuria and proteinuria. DIAGNOSES: Combined with clinical manifestations, laboratory testing, pathological changes of kidney and sequencing results, the patient was diagnosed as AS. INTERVENTIONS: The patient was treated with ACEI and tacrolimus drugs for 2 years, but continued to have hematuria and proteinuria. Thus, a genetic analysis was performed using next-generation sequencing in four affected members from the family. OUTCOMES: The findings revealed triple compound heterozygous mutation of COL4A4: three novel variations, c.1045C>T (p. R349X), c.3505+1G>A (splicing), and c.2165G>A (p. G722D). LESSONS: This study was novel in finding that a triple variant of the COL4A4 gene simultaneously in trans and in cis. The effects of multiple mutation sites and the type of gene mutation in AS were also underlined.
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Colágeno Tipo IV/genética , Nefrite Hereditária/genética , Criança , China/epidemiologia , Hematúria/genética , Sequenciamento de Nucleotídeos em Larga Escala , Humanos , Masculino , Mutação/genética , Nefrite Hereditária/etnologia , Linhagem , Proteinúria/genéticaRESUMO
Materials research usually relies on lengthy and largely trial-and-error methods, high-throughput technology has thereby emerged as an alternative method which is proven to be a simple, rapid, accurate and sensitive technique. Here, we presented a microfluidic platform with a set of 6 × 6 microarray chips for high-throughput synthesis and rapid screening the reaction conditions of biomedical materials. The core design of this platform is to generate concentration gradient inside microarray chips. Considering that calcium phosphates (CaP) are the most important inorganic constituents of biological hard tissues, different phases of calcium phosphates particles were synthesized with various morphogenesis when the reaction conditions such as Ca/P concentration ratio, NaOH concentration were screened using our platform. And this platform is universal and expected to apply to other systems for high-throughput screening and synthesis.
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As a left-handed helical structure, Z-DNA is biologically active and it may be correlated with transcription and genome stability. Until recently, it remained a significant challenge to control the B/Z-DNA transition under physiological conditions. The current study represents the first to reversibly control B/Z-DNA transition using cucurbit[7]uril-based supramolecular approach. It is demonstrated that cucurbit[7]uril can encapsulate the central butanediamine moiety [HN(CH2)4NH] and reverses Z-DNA caused by spermine back to B-DNA. The subsequent treatment with 1-adamantanamine disassembles the cucurbit[7]uril/spermine complex and readily induces reconversion of B- into Z-DNA. The DNA conformational change is unequivocally demonstrated using different independent methods. Direct evidence for supramolecular interactions involved in DNA conformational changes is further provided. These findings can therefore open a new route to control DNA helical structure in a reversible way.
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Developing a spatiotemporal-controlled platform with feasible synthesis and multifunctionality is highly desirable in the field of nanomedicine. Here, we present a near-infrared (NIR)-light-triggered approach to control the supramolecular assembly system for drug release and achieve synergistic chemo-photothermal therapy for cancer. A cucurbit[7]uril (CB[7]) stabilized gold nanostar (GNS) platform is designed to encapsulate the anticancer drug camptothecin (CPT) via host-guest chemistry. Importantly, CB[7] behaves not only as a surfactant to improve the stability of GNS in the aqueous solution but also as the cage for intermolecular assembly of CPT molecules. Moreover, without the competitive complexation, the drug release could be stimulated under NIR light irradiation. Synergistic treatment of cancer can be achieved by combining chemotherapy with the photothermal effect of GNS. This work develops a NIR-light-triggered cucurbituril-based drug-release approach that opens the door for remote control of drug release in the supramolecular assembly system.
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Antineoplásicos/uso terapêutico , Hidrocarbonetos Aromáticos com Pontes/química , Camptotecina/uso terapêutico , Ouro/química , Imidazóis/química , Raios Infravermelhos , Nanoestruturas/química , Neoplasias/tratamento farmacológico , Fotoquimioterapia/métodos , Animais , Antineoplásicos/química , Antineoplásicos/farmacocinética , Hidrocarbonetos Aromáticos com Pontes/uso terapêutico , Camptotecina/química , Camptotecina/farmacocinética , Terapia Combinada , Humanos , Hipertermia Induzida/métodos , Imidazóis/uso terapêutico , Células MCF-7 , Camundongos , Microscopia Confocal , Microscopia Eletrônica de Transmissão , Neoplasias/terapia , Espectrometria de Fluorescência , Distribuição Tecidual , Ensaios Antitumorais Modelo de XenoenxertoRESUMO
5-Formylcytosine (5fC) is identified as one of the key players in active DNA demethylation and also as an epigenetic mark in mammals, thus representing a novel attractive target to chemical intervention. The current study represents an attempt to develop a reversible 5fC-targeted intervention tool. A supramolecular aldehyde reactive probe was therefore introduced for selective conversion of the 5fC to 5fC-AD nucleotide. Using various methods, we demonstrate that cucurbit[7]uril (CB7) selectively targets the 5fC-AD nucleotide in DNA, however, the binding of CB7 to 5fC-AD does not affect the hydrogen bonding properties of natural nucleobases in duplex DNA. Importantly, CB7-driven host-guest chemistry has been applied for reversible intervention of a variety of 5fC-targeted biochemical reactions, including restriction endonuclease digestion, DNA polymerase elongation, and polymerase chain reaction. On the basis of the current study, the macrocyclic CB7 creates obstructions that, through steric hindrance, prevent the enzyme from binding to the substrate, whereas the CB7/5fC-AD host-guest interactions can be reversed by treatment with adamantanamine. Moreover, fragment- and site-specific identification of 5fC modification in DNA has been accomplished without sequence restrictions. These findings thus show promising potential of host-guest chemistry for DNA/RNA epigenetics.
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Adamantano/metabolismo , Aldeídos/metabolismo , Hidrocarbonetos Aromáticos com Pontes/metabolismo , Citosina/análogos & derivados , Imidazóis/metabolismo , Sondas Moleculares/metabolismo , Nucleosídeos/metabolismo , Adamantano/química , Aldeídos/química , Hidrocarbonetos Aromáticos com Pontes/química , Citosina/química , Citosina/metabolismo , DNA/química , DNA/metabolismo , Imidazóis/química , Sondas Moleculares/química , Estrutura Molecular , Nucleosídeos/químicaRESUMO
As the cucurbit[n]uril (CB[n]) homologue with the largest cavity size, cucurbit[10]uril (CB[10]) can encapsulate big guests to form interesting host-guest complexes/assemblies. Herein, we report the preparation and fluorescence properties of CB[10]-based [2]rotaxane (CB[10]·1) formed from cucurbit[10]uril and dumbbell-like guest 1. This [2]rotaxane (CB[10]·1) is assembled by CâO···N+ ion-dipole interactions between oxygen atoms of the carbonyl fringed portals of CB[10] and the positively charged pyridinium units of 1 via the slipping method under heating at 95 °C in DMSO. In contrast, other cucurbit[n]uril (CB[n], n = 6-8) homologues cannot form rotaxanes with 1 due to their smaller cavities. The dumbbell-like guest 1 is a poor emitter in DMSO. Interestingly, the formation of CB[10]·1 renders the restriction of intramolecular rotation of TPE, which features a strong fluorescent intensity, long lifetime, and high quantum yield. Furthermore, CB[10]·1 is shown to aggregate plate-like structures with various sizes in different solvents (DMSO, THF, or CHCl3), resulting in a stepwise aggregation-induced emission enhancement effect. This kind of CB[10]-based [2]rotaxane may be used to fabricate luminescent systems with unique emission properties.
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Supramolecular chemistry addresses intermolecular forces and consequently promises great flexibility and precision. Biological systems are often the inspirations for supramolecular research. The G-quadruplex (G4) belongs to one of the most important secondary structures in nucleic acids. Until recently, the supramolecular manipulation of the G4 has not been reported. The present study is the first to disclose a supramolecular switch for the reversible control of human telomere G4s. Moreover, this supramolecular switch has been successfully used to manipulate an enzymatic reaction. Using various methods, we show that cucurbit[7]uril preferably locks and encapsulates the positively charged piperidines of Razo through supramolecular interactions. They can switch the conformations of the DNA inhibitor between a flexible state and the rigid G4 and are therefore responsible for the reversible control of the thrombin activity. Thus, our findings open a promising route and exhibit potential applications in future studies of chemical biology.
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Hidrocarbonetos Aromáticos com Pontes/farmacologia , DNA/química , Quadruplex G/efeitos dos fármacos , Imidazóis/farmacologia , Trombina/química , Compostos Azo/química , Sequência de Bases , Hidrocarbonetos Aromáticos com Pontes/química , Humanos , Imidazóis/química , Simulação de Acoplamento Molecular , Piperidinas/química , Telômero/química , Telômero/efeitos dos fármacos , Trombina/metabolismoRESUMO
As the host possessing the largest cavity in the cucurbit[n]uril (CB[n]) family, CB[10] has previously displayed unusual recognition and assembly properties with guests but much remains to be explored. Herein, we present the recognition properties of CB[10] toward a series of bipyridinium guests including the tetracationic cyclophane known as blue box along with electron-rich guests and detail the influence of encapsulation on the charge-transfer interactions between guests. For the mono-bipyridinium guest (methylviologen, MV2+ ), CB[10] not only forms 1:1 and 1:2 inclusion complexes, but also enhances the charge-transfer interactions between methylviologen and dihydroxynaphthalene (HN) by mainly forming the 1:2:1 packed "sandwich" complex (CB[10]â 2 MV2+ â HN). For guest 1 with two bipyridinium units, an interesting conformational switching from linear to "U" shape is observed by adding catechol to the solution of CB[10] and the guest. For the tetracationic cyclophane-blue box, CB[10] forms a stable 1:1 inclusion complex; the two bipyridinium units tilt inside the cavity of CB[10] according to the X-ray crystal structure. Finally, a supramolecular "Russian doll" was built up by threading a guest through the cavities of both blue box and CB[10].
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The near infrared (NIR) absorption and average particle size of gold nanostars (GNSs) can be precisely controlled by varying the molar ratios of cucurbit[7]urils (CB[7]) and GNSs in aqueous solution. GNSs modified with CB[7] achieved high cargo loading with thermally activated release upon the NIR laser irradiation.