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1.
Angew Chem Int Ed Engl ; : e202409162, 2024 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-38860443

RESUMO

The application of supramolecular assembly (SA) with room temperature phosphorescence (RTP) in aqueous phase has the potential to revolutionize numerous fields. However, using simple molecules with crystalline RTP to construct SA with aqueous phase RTP is hardly possible from the standpoint of forces. The reason lies in that the transition from crystal to SA involves a structure transformation from highly stable to more dynamic state, leading to increased non-radiative deactivation pathways and silent RTP signal. Here, with the benefit of the confinement from the layered double hydroxide (LDH), various simple molecules (benzene derivatives) can successfully form metastable SA with aqueous phase RTP. The maximum of RTP lifetime and efficiency can reach 654.87 ms and 5.02 %, respectively. Mechanistic studies reveal the LDH energy trap can strengthen the intermolecular interaction, providing the prerequisite for the existence of metastable SA and appearance of aqueous phase RTP. The universality of this strategy will usher exploration into other multifunctional monomer, facilitating the development of SAs with aqueous phase RTP.

2.
Small ; 19(44): e2303497, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37376810

RESUMO

Homochiral supramolecular assembly (HSA) based on achiral molecules has provided important clues to understand the origin of biological homochirality from the aspect of symmetry breaking. However, planar achiral molecules still face the challenge of forming HSA due to the lack of driving force for twisted stacking, which is a prerequisite for homochirality. Here, with the benefit of the formation of 2D intercalated layered double hydroxide (LDH, host-guest nanomaterials) in vortex motion, planar achiral guest molecules can form the chiral units with spatially asymmetrical structure in the confinement space of LDH. Once the LDH is removed, these chiral units are in a thermodynamic non-equilibrium state, which can be amplified to HSA by self-replicating. Especially, the homochiral bias can be predicted in advance by controlling the vortex direction. Therefore, this study breaks the bottleneck of complicated molecular design and provides a new technology to achieve HSA made of planar achiral molecules with definite handedness.

3.
Am J Nephrol ; 54(11-12): 451-470, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37793354

RESUMO

INTRODUCTION: Dysbiosis of the intestinal microbiome and related metabolites have been observed in chronic kidney disease, yet their roles in idiopathic membranous nephropathy (IMN) are poorly understood. METHODS: In this study, we describe the variation of intestinal bacteria and fecal metabolites in patients with IMN in Chinese population. Stool samples were collected from 41 IMN patients at the beginning of diagnosis confirmation and 41 gender- and age-matched healthy control (HC). Microbial communities are investigated by sequencing of 16S rRNA genes and functional profiles predicted using Tax4Fun, and the correlation between intestinal bacteria and IMN clinical characteristics is also analyzed. Untargeted metabolomic analysis is performed to explore the relationship between colon's microbiota and fecal metabolites. RESULTS: IMN gastrointestinal microbiota demonstrates lower richness and diversity compared to HC, and exhibits a marked taxonomic and inferred functional dysbiosis when compared to HC. Some genera are closely related to the clinical parameters, such as Citrobacter and Akkermansia. Twenty characteristic microbial biomarkers are selected to establish a disease prediction model with a diagnostic accuracy of 93.53%. Fecal metabolomics shows that tryptophan metabolism is reduced in IMN patients but uremic toxin accumulation in feces is not noticeable. Fecal microbiota transplantation demonstrates that gut dysbiosis impairs gut permeability in microbiota-depleted mice and induces NOD-like receptor activation in the kidneys. CONCLUSIONS: Clarifying the changes in intestinal microbiota in IMN patients will help further know the pathogenesis of this disease, and microbiota-targeted biomarkers will provide a potentially powerful tool for diagnosing and treating IMN.


Assuntos
Microbioma Gastrointestinal , Glomerulonefrite Membranosa , Humanos , Camundongos , Animais , Microbioma Gastrointestinal/fisiologia , Disbiose , RNA Ribossômico 16S/genética , Biomarcadores
4.
Gynecol Endocrinol ; 39(1): 2283033, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-38010136

RESUMO

PURPOSE: To illustrate the results achieved by genes in premature ovarian insufficiency (POI) and collaborations in the field, and to explore key themes and future directions. METHODS: Articles and reviews related to POI genes published between 1990 and 2022 were retrieved from the Web of Science core collection (WoSCC) for the total bibliometric analysis. Tools were analyzed for publication, country, institution, journal, authors, reference, keywords, subject categories, funding agencies, and research hotspots using a bibliometric online analysis platform, Bibliographic Co-occurrence Matrix Builder (BICOMB), CiteSpace V, and VOSviewer. RESULTS: A total of 2,232 papers were included in this study. Articles were published in 52 countries, with the United States publishing the most, followed by China. A total of 308 institutions contributed to relevant publications. Shandong University published the most papers. Qin Y's team published the most relevant papers. Human reproduction and fertility and sterility are the two journals with the most papers. X-chromosome abnormalities, transcription factor mutations, and FMR1 genes are the directions of more POI, and DNA repair is the keyword of the research frontier in recent years. CONCLUSIONS: This study summarizes the relevant literature on POI gene research for the first time and analyzes the current hotspots and future trends in this field. The findings can further reveal the etiology, diagnosis, and treatment of POI, which is beneficial for researchers to grasp the genetic dynamics of POI women.


Assuntos
Menopausa Precoce , Insuficiência Ovariana Primária , Feminino , Humanos , Insuficiência Ovariana Primária/genética , Pesquisa , Bibliometria , China/epidemiologia , Proteína do X Frágil da Deficiência Intelectual
5.
Angew Chem Int Ed Engl ; 62(23): e202303063, 2023 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-37022095

RESUMO

The emergence of time-dependent phosphorescence color (TDPC) materials has taken information encryption to high-security levels. However, due to the only path of exciton transfer, it is almost impossible to obtain TDPC for chromophores with a single emission center. Theoretically, in inorganic-organic composites, the exciton transfer of organic chromophores depends on the inorganic structure. Here, we assign two structural effects to inorganic NaCl by metal (Mg2+ or Ca2+ or Ba2+ ) doping, which triggers the TDPC performance of carbon dots (CDs) with a single emission center. The resulting material is used for multi-level dynamic phosphorescence color 3D coding to achieve information encryption. The structural confinement activates the green phosphorescence of CDs; while the structural defect activates tunneling-related yellow phosphorescence. Such simply doped inorganic matrices can be synthesized using the periodic table of metal cations, endowing chromophores with tremendous control over TDPC properties. This demonstration extends the design view of dynamic luminescent materials.

6.
Molecules ; 27(19)2022 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-36235054

RESUMO

Carbon dots (CDs) have excellent optical properties, low toxicity and easy preparation, which have led to them being widely used in biomedicine, sensing and optical devices. However, although great progress has been made in the preparation of CDs, the detailed exploration of their photoluminescence (PL) mechanism is still under debate due to their complex structures and surface functionalities. Here, we proposed a single change in the pH of the synthesis condition, which had no effect on the CDs intrinsic core states and avoided the mutual influence of multiple PL origins. The m-phenylenediamine (m-PD) served as a carbon source, whose protonation degree determined the surface state of the resulting CDs and the accompanying fluorescence characteristics. The as-obtained CDs materials can be applied in the chemical sensor and anti-counterfeiting fields in a targeted manner. Therefore, our work not only contributes to the explanation of the CDs PL mechanism, but also obtains a series of CDs materials with controllable PL properties.


Assuntos
Carbono , Pontos Quânticos , Carbono/química , Pontos Quânticos/química
7.
J Phys Chem A ; 125(19): 4209-4215, 2021 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-33977714

RESUMO

A new strategy by manipulating the progress of triplet energy transfer (TET) is developed to realize adjustable multicolor and pure white emission. Donor phosphorescent molecules emits light when encapsulated into polyvinyl alcohol (PVA) through hydrogen bond interactions, and acceptor fluorescent molecules emits light when doped into PVA through cation-π interactions and hydrogen bond interactions. In addition, the triplet to singlet energy transfer process and mechanism are proved using the energy diagram and lifetime. The broadband emission color of the obtained composite film can be easily modulated by simply adjusting the amount and component of dyes, especially the white emission with CIE coordinates of (0.339, 0.337). This work provides a facile and versatile method for the development of multicolor and pure white-light-emitting diodes, which uses the interactions to light up luminescence properties, and can further aid in the wide development of applications for TET in various other fields.

8.
Langmuir ; 34(47): 14204-14214, 2018 11 27.
Artigo em Inglês | MEDLINE | ID: mdl-30380881

RESUMO

The nanoplatelet-filled polymer composite (NFPC) materials have received increasing attention because of their high strength-to-weight ratio and toughness. However, high-performance NFPC materials still face many challenges: (1) how to transfer the intrinsic extraordinary performance of individual nanoplatelets into highly ordered macroscale bulk materials; (2) how to obtain a strong interface bonding between polymer and nanoplatelet filler; and (3) how to truly reflect the structure of NFPC film. Here, to address these problems, the flow-induced assembly method is employed to fabricate the large-size continuous, flexible, highly oriented, and transparent NFPC film. During flow-induced orientation, nanoplatelet and polymer can be coassembling together to form a highly ordered layered structure with dozens of layers. On the other hand, the layered double hydroxide (LDH) nanosheet filler with single layer and abundant hydroxyl sites is prepared to strengthen interface by forming hydrogen bonds with polymers. To explore the effect of multiscale structure on property, carbon dots (CDs) are introduced to light up the inorganic nanoplatelet. By fixing and confining CDs in a rigid environment, the CD-LDH-based composite film shows excellent dual emission characteristics, which can be used to evaluate gas barrier, humidity, and temperature with direct visualization, high sensitivity, and easy to operation.

9.
Acta Biochim Biophys Sin (Shanghai) ; 50(12): 1190-1199, 2018 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-30383193

RESUMO

Colorectal cancer (CRC) is the one of the most common malignant tumors worldwide. Recent years, widespread long non-coding RNAs (lncRNAs) have been discovered and are known to regulate gene expression in cancers. However, the roles and underlying mechanisms of lncRNA in CRC remain largely unclear. Here, we firstly revealed that repression of lncRNA nuclear paraspeckle assembly transcript 1 (NEAT1) inhibited cell proliferation and migration in HCT116 cells and overexpression of NEAT1 promoted cell proliferation and migration in SW480 cells using CCK8 assay and transwell assay. Then, we found that suppression of NEAT1 increased the miR-196a-5p expression in HCT116 cells, while elevation of NEAT1 decreased the miR-196a-5p expression in SW480 cells using qPCR assay. Furthermore, miR-196a-5p could bind to the predicted binding site of NEAT1. We then found that miR-196a-5p was involved in the role of NEAT1 in CRCs. In addition, we demonstrated that miR-196a-5p mimics inhibited the glial cell-derived neurotrophic factor (GDNF) expression in HCT116 cells and meanwhile, miR-196a-5p inhibitor promoted GDNF expression in SW480 cells using qPCR and western blot analysis. Then, we proved that miR-196a-5p exerted its function via regulating GDNF expression in CRCs. Ultimately, our study demonstrated that NEAT1 exerted its role via miR-196a-5p/GDNF axis in CRCs. In summary, this work provided the first evidence of a NEAT1/miR-196a-5p/GDNF regulatory pathway in CRC.


Assuntos
Movimento Celular/genética , Proliferação de Células/genética , Regulação Neoplásica da Expressão Gênica , Fator Neurotrófico Derivado de Linhagem de Célula Glial/genética , MicroRNAs/genética , RNA Longo não Codificante/genética , Sequência de Bases , Linhagem Celular Tumoral , Sobrevivência Celular/genética , Neoplasias Colorretais/genética , Neoplasias Colorretais/metabolismo , Neoplasias Colorretais/patologia , Fator Neurotrófico Derivado de Linhagem de Célula Glial/metabolismo , Células HCT116 , Células HT29 , Humanos , Interferência de RNA , Homologia de Sequência do Ácido Nucleico
10.
Anal Chem ; 88(9): 4987-94, 2016 05 03.
Artigo em Inglês | MEDLINE | ID: mdl-27054376

RESUMO

It is a critical scientific challenge to improve the selectivity of cataluminescence (CTL). Chemisorbed oxygen on the surface of catalysts is one of the essential factors for catalytic oxidization of gaseous reactant molecules during the CTL process. Therefore, it is necessary to investigate the influence of chemisorbed oxygen on the CTL. There exists different chemisorbed oxygen content on the surface of Y2O3 and its precursor, layered rare-earth yttrium hydroxides (Y-NO3-LRHs). In this work, both of them were employed as catalyst models to catalytically oxidize common volatile organic compounds (VOCs) in order to explore the relationship between chemisorbed oxygen and CTL selectivity. It was found that LRHs demonstrated a superior selectivity toward ethyl ether in comparison with Y2O3. The mechanism study showed that only ethyl ether demonstrated the CTL behavior through the catalytical oxidation into CH3CHO* intermediates on the surface of LRHs, while no CTL emissions occurred for the other VOCs because the insufficient chemisorbed oxygen of LRHs was incapable of oxidizing these VOCs into CO2* intermediates. In addition, the luminescent rare-earth Eu(3+) ions were doped in Y-NO3-LRHs to further improve the CTL intensity of ethyl ether through the efficient energy transfer between CH3CHO* intermediates and Eu(3+) ions. Our work opens up a new route to improve CTL selectivity by tuning the chemisorbed oxygen on the surface of catalysts, different from the previous strategies of exploiting new solid catalysts or decreasing CTL reaction temperature.

11.
Anal Chem ; 88(16): 8188-93, 2016 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-27452577

RESUMO

Confinement effect in the layered double hydroxide (LDH) nanoreactors can control the reaction rate and disperse the fluorescence guest, which are promising to be introduced in optical sensing systems. In this work, an optical sensor has been fabricated by combining the confinement effect from the LDH nanoreactors with advantageous sensing performances of graphene quantum dots (GQDs). The mechanism indicated the LDHs with two dimensional (2D) confined space provided a stable microenvironment and acted as the disperse matrix to control the distribution of intercalated GQDs. Such a confinement effect may decrease the diffusion rate of hydroxyl radicals ((•)OH), and thus (•)OH with the short lifetime (10(-9) s) is annihilated during the diffusing process into the LDH interlayer galleries. As a result, the inherently existing interference from (•)OH for detection of NO2 was eliminated. Furthermore, a rapid and portable fluorescent paper sensor coated with the as-prepared GQD-LDHs for visual detection of NO2 gas was successfully developed. Our work provides a feasible method to remarkably improve the selectivity by virtue of confinement effect.

12.
Anal Bioanal Chem ; 408(30): 8787-8793, 2016 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26910825

RESUMO

This work proposed a cataluminescence (CTL) sensor for rapid and highly selective detection of diethyl ether using Mg-Al-layered double oxide (Mg-Al LDO). The linear range of the CTL intensity versus the concentration of diethyl ether was 0.1-8.0 mM, with a correlation coefficient (R) of 0.9915. The limit of detection (signal-to-noise ratio (S/N) = 3) was 0.02 mM. The half decay time was ~15 s, indicating a fast CTL process. The CTL sensor showed an excellent selectivity toward diethyl ether and good operational stability. Relative standard deviation (RSD) was less than 3 % in 20 consecutive measurements for diethyl ether. The CTL process was monitored by gas chromatography-mass spectrometry (GC/MS), pH indicator, and CTL spectrum. The results showed that the strong CTL signals were from the specific basic sites of Mg-Al LDO nanoparticle, which was further confirmed by temperature-programmed desorption of carbon dioxide (CO2-TPD). This work not only provides a facile approach to obtain a CTL sensor based on LDO but also systematically investigates the catalytic mechanism of LDO. Graphical abstract ᅟ.

13.
Langmuir ; 30(43): 12916-22, 2014 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-25285378

RESUMO

A highly oriented film was fabricated by layer-by-layer self-assembly of DNA and MgAl-layered double hydroxide nanosheets, and its application in chiroptical switch was demonstrated via intercalation and deintercalation of an achiral molecule into the DNA cavity. DNA molecules are prone to forming an ordered and dispersive state in the interlayer region of rigid layered double hydroxide (LDH) nanosheets as confirmed by scanning electron microscopy and atomic force microscopy. The induced chiroptical ultrathin film (UTF) is achieved via the intercalation of an achiral chromophore [5,10,15,20-tetrakis(4-N-methylpyridyl)porphine tetra(p-toluenesulfonate) (TMPyP)] into the spiral cavity of DNA stabilized in the LDH matrix [denoted as TMPyP-(DNA/LDH)20]. Fluorescence and circular dichroism spectroscopy are utilized to testify the intercalation of TMPyP into (DNA/LDH)20 UTF that involves two steps: the electrostatic binding of TMPyP onto the surface of (DNA/LDH)20 followed by intercalation into base pairs of DNA. In addition, the TMPyP-(DNA/LDH)20 UTF exhibits good reversibility and repeatability in induced optical chirality, based on the intercalation and deintercalation of TMPyP by alternate exposure to HCl and NH3/H2O vapor, which can be potentially used as a chiroptical switch in data storage.


Assuntos
DNA/química , Hidróxidos/química , Fenômenos Ópticos , Modelos Moleculares , Nanoestruturas/química , Conformação de Ácido Nucleico , Porfirinas/química
14.
Front Psychol ; 15: 1392167, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38831951

RESUMO

Aims: Prostate cancer patients face impaired body image and psychological distress during the diagnosis and treatment of the disease, which leads to changes in mood, cognition and behavior. Psychological resilience has been shown to buffer shocks and stresses from the disease. Therefore, this study investigates the relationship between family functioning and psychological resilience in prostate cancer patients and the mediating role of self-efficacy between family functioning and psychological resilience to provide a relevant theoretical basis for improving patients' psychological status by providing relevant theoretical basis. Method: Using a cross-sectional design, participants were 215 patients with prostate cancer admitted to and treated in a tertiary hospital in Jiangsu province, China. Questionnaires were administered using the general information questionnaire, the Connor-Davidson Resilience Scale (CD-RISC), the Family Adaptation, Partnership, Growth, Affection, and Resolution Index (APGAR), and the General Self-efficacy Scale (GSES). Data were analyzed using descriptive and correlational analyses and the bootstrap mediation test was used to test the effect relationship between the variables. Results: Family functioning, self-efficacy and psychological resilience were significantly and positively correlated (r = 0.526, P < 0.01; r = 0.378, P < 0.01; r = 0.358, P < 0.01). The mediating effect of psychological resilience between family functioning and psychological resilience was significant, accounting for 42.56%. Conclusion: Family function and self-efficacy have been shown to increase the level of psychological resilience in prostate cancer patients. Attention should be paid to the mental health problems of prostate cancer patients, early screening and intervention, and the use of patients' family resources to improve their confidence in recovering from the disease, thus increasing their psychological resilience and improving their mental health.

15.
J Agric Food Chem ; 72(11): 5944-5954, 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38466638

RESUMO

The objective of this study was to investigate the mechanism underlying nitric oxide (NO)-induced hypoxia-inducible factor-1α (HIF-1α) and its impact on yak muscle tenderness during post-mortem aging. The Longissimus thoracis et lumborum (LTL) muscle of yak were incubated at 4 °C for 0, 3, 6, 9, 12, 24, and 72 h after treatment with 0.9% saline, NO activator, or a combination of the NO activator and an HIF-1α inhibitor. Results indicated that elevated NO levels could increase HIF-1α transcription to achieve stable expression of HIF-1α protein (P < 0.05). Additionally, elevated NO triggered HIF-1α S-nitrosylation, which further upregulated the activity of key glycolytic enzymes, increased glycogen consumption, accelerated lactic acid accumulation, and decreased pH (P < 0.05). These processes eventually improved the tenderness of yak muscle during post-mortem aging (P < 0.05). The results demonstrated that NO-induced activation of HIF-1α S-nitrosylation enhanced glycolysis during post-mortem aging and provided a possible pathway for improving meat tenderness.


Assuntos
Subunidade alfa do Fator 1 Induzível por Hipóxia , Óxido Nítrico , Animais , Bovinos , Subunidade alfa do Fator 1 Induzível por Hipóxia/genética , Ácido Láctico/metabolismo
16.
J Pharm Anal ; 14(4): 100931, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38655401

RESUMO

Dynamic changes in gut dysbiosis and metabolomic dysregulation are associated with immune-complex glomerulonephritis (ICGN). However, an in-depth study on this topic is currently lacking. Herein, we report an ICGN model to address this gap. ICGN was induced via the intravenous injection of cationized bovine serum albumin (c-BSA) into Sprague-Dawley (SD) rats for two weeks, after which mycophenolate mofetil (MMF) and losartan were administered orally. Two and six weeks after ICGN establishment, fecal samples were collected and 16S ribosomal DNA (rDNA) sequencing and untargeted metabolomic were conducted. Fecal microbiota transplantation (FMT) was conducted to determine whether gut normalization caused by MMF and losartan contributed to their renal protective effects. A gradual decline in microbial diversity and richness was accompanied by a loss of renal function. Approximately 18 genera were found to have significantly different relative abundances between the early and later stages, and Marvinbryantia and Allobaculum were markedly upregulated in both stages. Untargeted metabolomics indicated that the tryptophan metabolism was enhanced in ICGN, characterized by the overproduction of indole and kynurenic acid, while the serotonin pathway was reduced. Administration of losartan and MMF ameliorated microbial dysbiosis and reduced the accumulation of indoxyl conjugates in feces. FMT using feces from animals administered MMF and losartan improved gut dysbiosis by decreasing the Firmicutes/Bacteroidetes (F/B) ratio but did not improve renal function. These findings indicate that ICGN induces serous gut dysbiosis, wherein an altered tryptophan metabolism may contribute to its progression. MMF and losartan significantly reversed the gut microbial and metabolomic dysbiosis, which partially contributed to their renoprotective effects.

17.
Phys Chem Chem Phys ; 15(41): 18217-22, 2013 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-24064552

RESUMO

The development of UV-shielding materials has attracted considerable attention in the field of coatings and sunscreen. This paper reports the UV-shielding mechanism of layered double hydroxide (LDH) materials in terms of chemical composition, structure and morphology, by using (LDH/PAA)n films (n stands for bilayer number) through alternate LBL assembly of LDH nanoparticles and poly(acrylic acid) (PAA) on quartz substrates as a model system. A combination investigation based on experimental and theoretical study demonstrates that the maximum UV scattering can be achieved when λ/d ≈ 1.98; the introduction of Zn element is an effective way to tune the electron structure, band gap, transition mode and resulting UV-shielding property of LDH materials. A UV-shielding efficiency as high as 95% can be obtained by modulating the particle size, composition and thickness of the LDHs. Furthermore, the UV anti-aging capacity of LDH-modified bitumen was studied, which demonstrates a large improvement in UV-resistance performance of bitumen by the incorporation of LDH materials. Therefore, this work systematically discloses the relationship between UV-shielding property and chemical/structural parameters of LDH materials, which can be potentially used as anti-aging agents in various organic matrices and polymer areas.

18.
ACS Nano ; 17(4): 3838-3846, 2023 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-36779509

RESUMO

Chiral supramolecular assembly (CSA) based on achiral molecules has provided important clues to understand the origin of biological chirality. However, a simple achiral monomer faces the challenge of chiral stacking with the absence of a chiral resource. The difficulty is that simple achiral monomer lacks steric repulsion to provide asymmetry during hierarchical assembly, which is a prerequisite for chiral stacking with an angle. Moreover, during chiral stacking of achiral molecules or units, the right-handed and left-handed chiral supramolecular isomers (CSIs) are equally formed due to the mirror-imaged conformation, which leads to chirality silence. Here, with the benefit of two-dimensional confinement space of layered double hydroxide (LDH), simple achiral molecules can be arranged to staggered bilayer arrays by imprinting the topological structure of LDH. Once LDH is removed, these staggered arrays can form asymmetric living seeds, which can further elongate to living units with the advantage of living supramolecular polymerization (LSP) by following off-pathway. Due to the asymmetry of living units, the possible chiral stacking outcomes, CSIs, are not mirror-imaged. With the increase of the molecular number in living units, the energy difference between CSIs can be amplified by self-replication of LSP, leading to handedness preference. Thus, the detectable CSA is mainly derived from the CSI with energetically favored hierarchical structure. Thus, our strategy breaks the stereotype that the complex molecular structure and symmetry breaking mechanism are necessary for the formation of detectable CSA by achiral molecules.

19.
Int J Biol Macromol ; 234: 123650, 2023 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-36791940

RESUMO

Inspired by the natural nacre structure, we propose a new strategy to fabricate mineralized, multiple crosslinked hydrogel membranes with the "rigid silica in soft polymer" nacre-like structure. In-situ SiO2 nanoparticles (NPs) and polyvinyl alcohol/sodium alginate (PVA/NaAlg) are used to simulate the rigid "bricks" and soft "mortar" compositions of nacre, respectively. The nacre-like mineralized (PVA/CaAlg/SiO2) membrane showed a higher tensile strength of 4.1 ± 0.08 MPa, excellent pure water flux of 170 ± 3 L/m2h, and an oil/water rejection rate of 99 %. The interwoven hierarchal structure, similar to nacre, was determined by SEM analysis. In addition, incorporating SiO2 NPs increases the anti-swelling, roughness, and hydrophilicity of the membranes. PVA/CaAlg/SiO2 membrane exhibited excellent superhydrophilicity (WCA value was 0°) and superoleophobicity underwater (OCA value was 162°). PVA/CaAlg/SiO2 membrane also showed excellent separation performance for water-soluble organic pollutants and can be used for dye separation with rejection efficiencies of 99.5 %, 99.1 %, and 98.3 % for Congo red (CR), Alizarin red (AR), and Sunset yellow (SY), respectively. Moreover, PVA/CaAlg/SiO2 membrane had outstanding long-term filtration and antifouling performance. The biomineralization-inspired structure provides a promising technique that can be used to prepare high-performance organic-inorganic membranes with great promise for wastewater separation application.


Assuntos
Nácar , Dióxido de Silício , Dióxido de Silício/química , Nácar/química , Biomimética/métodos , Álcool de Polivinil/química , Resistência à Tração
20.
ACS Appl Mater Interfaces ; 15(27): 32772-32782, 2023 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-37390488

RESUMO

The successful preparation of supramolecular block copolymers (SBCPs) by living supramolecular assembly technology requires two kinetic systems in which both the seed (nucleus) and heterogenous monomer providers are in non-equilibrium. However, employing simple monomers to construct the SBCPs via this technology is almost impossible because the low spontaneous nucleation barrier of simple molecules prevents the formation of kinetic states. Here, with the help of confinement from layered double hydroxide (LDH), various simple monomers successfully form living supramolecular co-assemblies (LSCA). LDH overcomes a considerable energy barrier to obtain living seeds to support the growth of the inactivated second monomer. The ordered LDH topology is sequentially mapped to the seed, second monomer, and binding sites. Thus, the multidirectional binding sites are endowed with the ability to branch, making the branch length of dendritic LSCA reach its maximum value of 3.5 cm so far. The strategy of universality will guide exploration into the development of multi-function and multi-topology advanced supramolecular co-assemblies.

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