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1.
Cell ; 184(5): 1362-1376.e18, 2021 03 04.
Artículo en Inglés | MEDLINE | ID: mdl-33545087

RESUMEN

Lungfishes are the closest extant relatives of tetrapods and preserve ancestral traits linked with the water-to-land transition. However, their huge genome sizes have hindered understanding of this key transition in evolution. Here, we report a 40-Gb chromosome-level assembly of the African lungfish (Protopterus annectens) genome, which is the largest genome assembly ever reported and has a contig and chromosome N50 of 1.60 Mb and 2.81 Gb, respectively. The large size of the lungfish genome is due mainly to retrotransposons. Genes with ultra-long length show similar expression levels to other genes, indicating that lungfishes have evolved high transcription efficacy to keep gene expression balanced. Together with transcriptome and experimental data, we identified potential genes and regulatory elements related to such terrestrial adaptation traits as pulmonary surfactant, anxiolytic ability, pentadactyl limbs, and pharyngeal remodeling. Our results provide insights and key resources for understanding the evolutionary pathway leading from fishes to humans.


Asunto(s)
Adaptación Biológica , Evolución Biológica , Peces/genética , Secuenciación Completa del Genoma , Aletas de Animales/anatomía & histología , Aletas de Animales/fisiología , Animales , Extremidades/anatomía & histología , Extremidades/fisiología , Peces/anatomía & histología , Peces/clasificación , Peces/fisiología , Filogenia , Fenómenos Fisiológicos Respiratorios , Sistema Respiratorio/anatomía & histología , Vertebrados/genética
2.
Nucleic Acids Res ; 51(D1): D603-D610, 2023 01 06.
Artículo en Inglés | MEDLINE | ID: mdl-36399496

RESUMEN

With an ever-increasing amount of (meta)genomic data being deposited in sequence databases, (meta)genome mining for natural product biosynthetic pathways occupies a critical role in the discovery of novel pharmaceutical drugs, crop protection agents and biomaterials. The genes that encode these pathways are often organised into biosynthetic gene clusters (BGCs). In 2015, we defined the Minimum Information about a Biosynthetic Gene cluster (MIBiG): a standardised data format that describes the minimally required information to uniquely characterise a BGC. We simultaneously constructed an accompanying online database of BGCs, which has since been widely used by the community as a reference dataset for BGCs and was expanded to 2021 entries in 2019 (MIBiG 2.0). Here, we describe MIBiG 3.0, a database update comprising large-scale validation and re-annotation of existing entries and 661 new entries. Particular attention was paid to the annotation of compound structures and biological activities, as well as protein domain selectivities. Together, these new features keep the database up-to-date, and will provide new opportunities for the scientific community to use its freely available data, e.g. for the training of new machine learning models to predict sequence-structure-function relationships for diverse natural products. MIBiG 3.0 is accessible online at https://mibig.secondarymetabolites.org/.


Asunto(s)
Genoma , Genómica , Familia de Multigenes , Vías Biosintéticas/genética
3.
J Am Chem Soc ; 146(10): 6706-6720, 2024 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-38421812

RESUMEN

Two-dimensional (2D) halide perovskites are exquisite semiconductors with great structural tunability. They can incorporate a rich variety of organic species that not only template their layered structures but also add new functionalities to their optoelectronic characteristics. Here, we present a series of new methylammonium (CH3NH3+ or MA)-based 2D Ruddlesden-Popper perovskites templated by dimethyl carbonate (CH3OCOOCH3 or DMC) solvent molecules. We report the synthesis, detailed structural analysis, and characterization of four new compounds: MA2(DMC)PbI4 (n = 1), MA3(DMC)Pb2I7 (n = 2), MA4(DMC)Pb3I10 (n = 3), and MA3(DMC)Pb2Br7 (n = 2). Notably, these compounds represent unique structures with MA as the sole organic cation both within and between the perovskite sheets, while DMC molecules occupy a tight space between the MA cations in the interlayer. They form hydrogen-bonded [MA···DMC···MA]2+ complexes that act as spacers, preventing the perovskite sheets from condensing into each other. We report one of the shortest interlayer distances (∼5.7-5.9 Å) in solvent-incorporated 2D halide perovskites. Furthermore, the synthesized crystals exhibit similar optical characteristics to other 2D perovskite systems, including narrow photoluminescence (PL) signals. The density functional theory (DFT) calculations confirm their direct-band-gap nature. Meanwhile, the phase stability of these systems was found to correlate with the H-bond distances and their strengths, decreasing in the order MA3(DMC)Pb2I7 > MA4(DMC)Pb3I10 > MA2(DMC)PbI4 ∼ MA3(DMC)Pb2Br7. The relatively loosely bound nature of DMC molecules enables us to design a thermochromic cell that can withstand 25 cycles of switching between two colored states. This work exemplifies the unconventional role of the noncharged solvent molecule in templating the 2D perovskite structure.

4.
Neurobiol Dis ; 192: 106425, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38296113

RESUMEN

BACKGROUND: Epilepsy is a chronic neurologic disorder characterized by abnormal functioning of brain networks, making it a complex research topic. Recent advancements in neuroimaging technology offer an effective approach to unraveling the intricacies of the human brain. Within different types of epilepsy, there is growing recognition regarding ongoing changes in the default mode network (DMN). However, little is known about the shared and distinct alterations of static functional connectivity (sFC) and dynamic functional connectivity (dFC) in DMN among epileptic subtypes, especially in children with epilepsy. METHODS: Here, 110 children with epilepsy at a single center, including idiopathic generalized epilepsy (IGE), frontal lobe epilepsy (FLE), temporal lobe epilepsy (TLE), and parietal lobe epilepsy (PLE), as well as 84 healthy controls (HC) underwent resting-state functional magnetic resonance imaging (fMRI) scan. We investigated both sFC and dFC between groups of the DMN. RESULTS: Decreased static and dynamic connectivity within the DMN subsystem were shared by all subtypes. In each epilepsy subtype, children with epilepsy displayed significant and distinct patterns of DMN connectivity compared to the control group: the IGE group showed reduced interhemispheric connectivity, the FLE group consistently demonstrated disturbances in frontal region connectivity, the TLE group exhibited significant disruptions in hippocampal connectivity, and the PLE group displayed a notable decrease in parietal-temporal connectivity within the DMN. Some state-specific FC disruptions (decreased dFC) were observed in each epilepsy subtype that cannot detect by sFC. To determine their uniqueness within specific subtypes, bootstrapping methods were employed and found the significant results (IGE: between PCC and bilateral precuneus, FLE: between right middle frontal gyrus and bilateral middle temporal gyrus, TLE: between left Hippocampus and right fusiform, PLE: between left angular and cingulate cortex). Furthermore, only children with IGE exhibited dynamic features associated with clinical variables. CONCLUSIONS: Our findings highlight both shared and distinct FC alterations within the DMN in children with different types of epilepsy. Furthermore, our work provides a novel perspective on the functional alterations in the DMN of pediatric patients, suggesting that combined sFC and dFC analysis can provide valuable insights for deepening our understanding of the neuronal mechanism underlying epilepsy in children.


Asunto(s)
Epilepsia Generalizada , Epilepsia del Lóbulo Temporal , Epilepsia , Humanos , Niño , Imagen por Resonancia Magnética/métodos , Red en Modo Predeterminado , Mapeo Encefálico/métodos , Encéfalo/diagnóstico por imagen , Epilepsia/diagnóstico por imagen , Inmunoglobulina E
5.
J Transl Med ; 22(1): 425, 2024 May 04.
Artículo en Inglés | MEDLINE | ID: mdl-38704596

RESUMEN

BACKGROUND: The intricate etiology of autoimmune liver disease (AILD) involves genetic, environmental, and other factors that yet to be completely elucidated. This study comprehensively assessed the causal association between genetically predicted modifiable risk factors and AILD by employing Mendelian randomization. METHODS: Genetic variants associated with 29 exposure factors were obtained from genome-wide association studies (GWAS). Genetic association data with autoimmune hepatitis (AIH), primary biliary cholangitis (PBC) and primary sclerosing cholangitis (PSC) were also obtained from publicly available GWAS. Univariate and multivariate Mendelian randomization analyses were performed to identify potential risk factors for AILD. RESULTS: Genetically predicted rheumatoid arthritis (RA) (OR = 1.620, 95%CI 1.423-1.843, P = 2.506 × 10- 13) was significantly associated with an increased risk of AIH. Genetically predicted smoking initiation (OR = 1.637, 95%CI 1.055-2.540, P = 0.028), lower coffee intake (OR = 0.359, 95%CI 0.131-0.985, P = 0.047), cholelithiasis (OR = 1.134, 95%CI 1.023-1.257, P = 0.017) and higher C-reactive protein (CRP) (OR = 1.397, 95%CI 1.094-1.784, P = 0.007) were suggestively associated with an increased risk of AIH. Genetically predicted inflammatory bowel disease (IBD) (OR = 1.212, 95%CI 1.127-1.303, P = 2.015 × 10- 7) and RA (OR = 1.417, 95%CI 1.193-1.683, P = 7.193 × 10- 5) were significantly associated with increased risk of PBC. Genetically predicted smoking initiation (OR = 1.167, 95%CI 1.005-1.355, P = 0.043), systemic lupus erythematosus (SLE) (OR = 1.086, 95%CI 1.017-1.160, P = 0.014) and higher CRP (OR = 1.199, 95%CI 1.019-1.410, P = 0.028) were suggestively associated with an increased risk of PBC. Higher vitamin D3 (OR = 0.741, 95%CI 0.560-0.980, P = 0.036) and calcium (OR = 0.834, 95%CI 0.699-0.995, P = 0.044) levels were suggestive protective factors for PBC. Genetically predicted smoking initiation (OR = 0.630, 95%CI 0.462-0.860, P = 0.004) was suggestively associated with a decreased risk of PSC. Genetically predicted IBD (OR = 1.252, 95%CI 1.164-1.346, P = 1.394 × 10- 9), RA (OR = 1.543, 95%CI 1.279-1.861, P = 5.728 × 10- 6) and lower glycosylated hemoglobin (HbA1c) (OR = 0.268, 95%CI 0.141-0.510, P = 6.172 × 10- 5) were positively associated with an increased risk of PSC. CONCLUSIONS: Evidence on the causal relationship between 29 genetically predicted modifiable risk factors and the risk of AIH, PBC, and PSC is provided by this study. These findings provide fresh perspectives on the management and prevention strategies for AILD.


Asunto(s)
Predisposición Genética a la Enfermedad , Estudio de Asociación del Genoma Completo , Análisis de la Aleatorización Mendeliana , Humanos , Factores de Riesgo , Enfermedades Autoinmunes/genética , Hepatitis Autoinmune/genética , Hepatitis Autoinmune/epidemiología , Polimorfismo de Nucleótido Simple/genética , Causalidad , Hepatopatías/genética , Cirrosis Hepática Biliar/genética
6.
Opt Express ; 32(11): 19019-19033, 2024 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-38859046

RESUMEN

In order to guarantee the information of the W-band wireless communication system from the physical layer, this paper proposes the sliced chaotic encrypted (SCE) transmission scheme based on key masked distribution (KMD). The scheme improves the security of free space communication in the W-band millimeter-wave wireless data transmission system. In this scheme, the key information is embedded into the random position of the ciphertext information, and then the ciphertext carrying the key information is encrypted by multi-dimensional chaos. Chaotic system 1 constructs a three-dimensional discrete chaotic map for implementing KMD. Chaotic system 2 constructs complex nonlinear dynamic behavior through the coupling of two neurons, and the masking factor generated is used to realize SCE. In this paper, the transmission of 16QAM signals in a 4.5 m W-band millimeter-wave wireless communication system with a rate of 40 Gb/s is proved by experiments, and the performance of the system is analyzed. When the input optical power is 5 dBm, the bit error rate (BER) of the legitimate encrypted receiver is 1.23 × 10-3. When the offset of chaotic sequence x and chaotic sequence y is 100, their BERs are more than 0.21. The key space of the chaotic system reaches 10192, which can effectively prevent illegal attacks and improve the security performance of the system. The experimental results show that the scheme can effectively distribute the keys and improve the security of the system. It has great application potential in the future of W-band millimeter-wave wireless secure communication.

7.
Chemistry ; 30(30): e202400281, 2024 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-38507278

RESUMEN

Solid-state glass nanopipettes provide a promising confined space that offers several advantages such as controllable size, simple preparation, low cost, good mechanical stability, and good thermal stability. These advantages make them an ideal choice for various applications such as biosensors, DNA sequencing, and drug delivery. In this review, we first delve into the functionalized nanopipettes for sensing various analytes and the methods used to develop detection means with them. Next, we provide an in-depth overview of the advanced functionalization methodologies of nanopipettes based on diversified chemical kinetics. After that, we present the latest state-of-the-art achievements and potential applications in detecting a wide range of targets, including ions, molecules, biological macromolecules, and single cells. We examine the various challenges that arise when working with these targets, as well as the innovative solutions developed to overcome them. The final section offers an in-depth overview of the current development status, newest trends, and application prospects of sensors. Overall, this review provides a comprehensive and detailed analysis of the current state-of-the-art functionalized nanopipette perception sensing and development of detection means and offers valuable insights into the prospects for this exciting field.

8.
Cell Mol Neurobiol ; 44(1): 16, 2024 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-38198062

RESUMEN

Circular RNA circSKA3 (spindle and kinetochore-related complex subunit 3) has been identified as a prognostic factor in ischemic stroke. The objective of this study was to investigate the association of circSKA3 with the risk of extracranial artery stenosis (ECAS) and plaque instability in patients with ischemic stroke. We constructed a competing endogenous RNA (ceRNA) network regulated by circSKA3 based on differentially expressed circRNAs and mRNAs between five patients and five controls. Gene Ontology (GO) analysis was performed on the 65 mRNAs within the network, revealing their primary involvement in inflammatory biological processes. A total of 284 ischemic stroke patients who underwent various imaging examinations were included for further analyses. Each 1 standard deviation increase in the log-transformed blood circSKA3 level was associated with a 56.3% increased risk of ECAS (P = 0.005) and a 142.1% increased risk of plaque instability (P = 0.005). Patients in the top tertile of circSKA3 had a 2.418-fold (P < 0.05) risk of ECAS compared to the reference group (P for trend = 0.02). CircSKA3 demonstrated a significant but limited ability to discriminate the presence of ECAS (AUC = 0.594, P = 0.015) and unstable carotid plaques (AUC = 0.647, P = 0.034). CircSKA3 improved the reclassification power for ECAS (NRI: 9.86%, P = 0.012; IDI: 2.97%, P = 0.007) and plaque instability (NRI: 36.73%, P = 0.008; IDI: 7.05%, P = 0.04) beyond conventional risk factors. CircSKA3 played an important role in the pathogenesis of ischemic stroke by influencing inflammatory biological processes. Increased circSKA3 was positively associated with the risk of ECAS and plaque instability among ischemic stroke patients.


Asunto(s)
Accidente Cerebrovascular Isquémico , Humanos , Constricción Patológica , Accidente Cerebrovascular Isquémico/complicaciones , Accidente Cerebrovascular Isquémico/genética , Factores de Riesgo , Ontología de Genes , ARN Circular , ARN Mensajero , Arterias
9.
Planta Med ; 2024 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-38857860

RESUMEN

5(S)-5-carboxystrictosidine (5-CS) is a compound found in the root of Mappianthus iodoides, a traditional Chinese medicine used for the treatment of coronary artery disease. The aim of the present study was to investigate the protective effect of 5-CS against oxidative stress-induced apoptosis in H9c2 cardiomyocytes and the underlying mechanisms. 5-CS pretreatment significantly protected against H2O2-induced cell death, LDH leakage and malondialdehyde (MDA) production which are indicators for oxidative stress injury. 5-CS also enhanced the activity of SOD and CAT. In addition, 5-CS pretreatment significantly inhibited H2O2-induced apoptosis, as determined by flow cytometer, suppressed the activity of caspase-3 and caspase-9 and attenuated the activation of cleaved caspase-3 and caspase-9. 5-CS also increased Akt and ERK activation altered by H2O2 using Western blot analysis. The PI3K-specific inhibitor LY294002 abolished 5-CS-induced Akt activation. The ERK-specific inhibitor PD98059 abolished 5-CS-induced ERK activation. Both LY294002 and PD98059 attenuated the protective effect of 5-CS on H9c2 cardiomyocytes against H2O2-induced apoptosis and cell death. Taken together, these results demonstrate that 5-CS prevents H2O2-induced oxidative stress injury in H9c2 cells by enhancing the activity of the endogenous antioxidant enzymes, inhibiting apoptosis, and modulating PI3K/Akt and ERK signaling pathways.

10.
Psychol Res ; 88(3): 880-891, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38282131

RESUMEN

Verbal praise is often used to improve prospective memory performance in daily life. According to the motivation cognitive model, the promotional effect of verbal praise on prospective memory may depend largely on redeploying attentional resources, so its promotional effect is likely to be influenced by attention. Two groups of college students (n = 128, n = 117) participated in two experimental studies that examined this hypothesis. Experiment 1 manipulated attention load by changing the difficulty of the ongoing tasks to focus on the effect of verbal praise on prospective memory under different attention load conditions. The results showed that verbal praise promoted prospective memory performance under both attentional load conditions (low, high), but verbal praise mainly promoted the prospective component when the attentional load was low, meanwhile, verbal praise mainly promoted the retrospective component when the attention load was high. Experiment 2 altered the dependence of prospective memory tasks on attentional resources by manipulating the cue focality, further exploring the promotional effect of verbal praise on prospective memory with different types of cues under the low attention load condition. The results showed that verbal praise only promoted prospective memory when non-focal cues were used. The results of this study partially verified the motivation cognitive model.


Asunto(s)
Memoria Episódica , Humanos , Estudios Retrospectivos , Señales (Psicología) , Atención , Cognición
11.
Chaos ; 34(6)2024 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-38865094

RESUMEN

A chaotic map with two-dimensional offset boosting is exhaustively studied, which is derived from the Lozi map and shows the controllability of amplitude control. The mechanism of two-dimensional offset boosting is revealed based on the cancelation of offset-involved feedback terms. Furthermore, the coexistence of homogeneous multistability and heterogeneous multistability is disclosed when the offset boosting turns to the initial condition. It is also found that the independent constant term rescales the amplitude of all the sequences without changing the Lyapunov exponents. More strikingly, the parameters for amplitude control and offset boosting are bound together introducing hybrid control. The circuit implementation based on the microcontroller unit is used to validate the theoretical analysis and numerical simulations. This chaotic map is applied for particle swarm optimization showing its stronger performance and robustness in solving optimization problems.

12.
Chaos ; 34(3)2024 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-38447937

RESUMEN

Offset boosting plays an important role in chaos application in electronic engineering. A direct variable substitution typically will destroy the dynamics of a discrete map even though the initial condition is well considered. The internal fundamental reason is that the left-hand side of a discrete system does not have the dimension of variable differentiation (DVD) like the one of a continuous system. When the key property of DVD is completely preserved, the offset boosting based on a parameter or the initial condition can be reasonably achieved like in a differential system. Consequently, by the initial condition-oriented offset boosting, flexible multistability like attractor self-reproducing or attractor doubling can be further realized. A circuit experiment is completed for the verification of reliable offset boosting. The systematic exploration of offset boosting in a map will cast a new light on chaos regulation and attractor transportation in a discrete map. As a simple case, a two-dimensional Hénon map is taken as the example demonstrating the achievement of offset boosting via the parameter or initial condition.

13.
Eur Arch Otorhinolaryngol ; 281(7): 3535-3545, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38353769

RESUMEN

OBJECTIVE: The objectives of this study are twofold: first, to visualize the structure of malformed cochleae through image reconstruction; and second, to develop a predictive model for postoperative outcomes of cochlear implantation (CI) in patients diagnosed with cochlear hypoplasia (CH) and incomplete partition (IP) malformation. METHODS: The clinical data from patients diagnosed with cochlear hypoplasia (CH) and incomplete partition (IP) malformation who underwent cochlear implantation (CI) at Beijing Tongren Hospital between January 2016 and August 2020 were collected. Radiological features were analyzed through 3D segmentation of the cochlea. Postoperative auditory speech rehabilitation outcomes were evaluated using the Categories of Auditory Performance (CAP) and the Speech Intelligibility Rating (SIR). This study aimed to investigate the relationship between cochlear parameters and postoperative outcomes. Additionally, a predictive model for postoperative outcomes was developed using the K-nearest neighbors (KNN) algorithm. RESULTS: In our study, we conducted feature selection by using patients' imaging and audiological attributes. This process involved methods such as the removal of missing values, correlation analysis, and chi-square tests. The findings indicated that two specific features, cochlear volume (V) and cochlear canal length (CDL), significantly contributed to predicting the outcomes of hearing and speech rehabilitation for patients with inner ear malformations. In terms of hearing rehabilitation, the KNN classification achieved an accuracy of 93.3%. Likewise, for speech rehabilitation, the KNN classification demonstrated an accuracy of 86.7%. CONCLUSION: The measurements obtained from the 3D reconstruction model hold significant clinical relevance. Despite the considerable variability in cochlear morphology across individuals, radiological features remain effective in predicting cochlear implantation (CI) prognosis for patients with inner ear malformations. The utilization of 3D segmentation techniques and the developed predictive model can assist surgeons in conducting preoperative cochlear structural measurements for patients with inner ear malformations. This, in turn, can offer a more informed perspective on the anticipated outcomes of cochlear implantation.


Asunto(s)
Cóclea , Implantación Coclear , Aprendizaje Automático , Humanos , Implantación Coclear/métodos , Masculino , Femenino , Cóclea/anomalías , Cóclea/diagnóstico por imagen , Cóclea/cirugía , Lactante , Resultado del Tratamiento , Preescolar , Oído Interno/anomalías , Oído Interno/cirugía , Oído Interno/diagnóstico por imagen , Imagenología Tridimensional , Estudios Retrospectivos , Niño
14.
Int J Psychol ; 2024 May 30.
Artículo en Inglés | MEDLINE | ID: mdl-38816955

RESUMEN

Studies have shown that facial recognition among racial groups exhibits not only an other-race effect but also an other-ethnicity effect within the same racial group. To explore differences in facial recognition and visual scanning patterns due to the other-ethnicity effect, behavioural and eye-movement data were used to investigate the other-ethnicity effect in the facial perception of Tibetan and Han Chinese individuals and whether the visual scanning patterns varied between them. Behavioural data revealed an other-ethnicity effect on facial recognition of Tibetan and Han individuals. Eye-movement data indicated that Tibetan and Han individuals fixated more on the eye and mouth regions when recognising Han faces and on the eye and nose regions when recognising Tibetan faces. The other-ethnicity effect appeared to influence facial recognition in Tibetan and Han individuals, who adopted similar visual scanning patterns when scanning the faces of individuals of their own ethnicity and those of other ethnicities.

15.
Angew Chem Int Ed Engl ; 63(7): e202319022, 2024 Feb 12.
Artículo en Inglés | MEDLINE | ID: mdl-38153357

RESUMEN

Cycloheptatrienyl (tropyl) molecules are representative non-alternant hydrocarbons that offer interesting chemistry because of their unique structures and properties. However, there have been a limited number of polycyclic aromatic tropyl cations and radicals reported in the literature. Herein, we report the synthesis of a series of azahomocorannulene derivatives, where the key reactions are a 1,3-dipolar cycloaddition of polycyclic aromatic azomethine ylides with dibenzotropone and a subsequent palladium-catalyzed cyclization. X-ray diffraction analysis revealed that the obtained azahomocorannulenyl cation and radical adopt planar structures and exhibit unique packing structures. Their electronic and optical properties were investigated experimentally and theoretically to reveal their aromatic character.

16.
J Am Chem Soc ; 145(23): 12475-12486, 2023 Jun 14.
Artículo en Inglés | MEDLINE | ID: mdl-37267593

RESUMEN

Artificial molecular machines have captured the full attention of the scientific community since Jean-Pierre Sauvage, Fraser Stoddart, and Ben Feringa were awarded the 2016 Nobel Prize in Chemistry. The past and current developments in molecular machinery (rotaxanes, rotors, and switches) primarily rely on organic-based compounds as molecular building blocks for their assembly and future development. In contrast, the main group chemical space has not been traditionally part of the molecular machine domain. The oxidation states and valency ranges within the p-block provide a tremendous wealth of structures with various chemical properties. Such chemical diversity─when implemented in molecular machines─could become a transformative force in the field. Within this context, we have rationally designed a series of NH-bridged acyclic dimeric cyclodiphosphazane species, [(µ-NH){PE(µ-NtBu)2PE(NHtBu)}2] (E = O and S), bis-PV2N2, displaying bimodal bifurcated R21(8) and trifurcated R31(8,8) hydrogen bonding motifs. The reported species reversibly switch their topological arrangement in the presence and absence of anions. Our results underscore these species as versatile building blocks for molecular machines and switches, as well as supramolecular chemistry and crystal engineering based on cyclophosphazane frameworks.

17.
Anal Chem ; 95(35): 13376-13384, 2023 09 05.
Artículo en Inglés | MEDLINE | ID: mdl-37603691

RESUMEN

It is important to quantify multiple biomarkers in a single run due to the advantages of precious samples and diagnostic accuracy. Based on the distinguishability of two types of current signals from single particle electrochemical collision (SPEC), step-type current transients produced by Pt nanoparticles (PtNPs) catalyzed hydrazine oxidation and peak-type current transients produced by Ag nanoparticles (AgNPs) oxidation, a kind of multiplex immunoassay of target microRNAs (miRNA-21 and Let-7a) have been established during SPEC in a single run. When the single-stranded DNA (ssDNA1) that was perfectly complementary to miRNA-21 was coupled to the surface of PtNPs, the SPEC of PtNPs electrocatalysis was inhibited and the step-type current transients disappeared, while the single-stranded DNA (ssDNA2) that was perfectly complementary to Let-7a was coupled to the surface of AgNPs, the SPEC of AgNPs oxidation was inhibited, and the peak-type current transients disappeared, thus the signals were in the "off" state at this time. After that, miRNA-21 and Let-7a were added into solution, complementary base pairing disrupted the weak DNA-NP interaction and restored the electrocatalysis of PtNPs and the electrooxidation of AgNPs, and the step-type current signals and peak-type current signals were in the "on" state. Moreover, the frequencies from two different recovered signals (PtNPs catalysis and AgNPs oxidation) corresponded to the amount of added miRNA-21 and Let-7a, thus a multiplex immunoassay method for dual quantification of miRNA-21 and Let-7a in a single run was established.


Asunto(s)
Antígenos de Grupos Sanguíneos , Nanopartículas del Metal , MicroARNs , ADN de Cadena Simple , Plata , Antígenos O
18.
Anal Chem ; 95(32): 11978-11987, 2023 08 15.
Artículo en Inglés | MEDLINE | ID: mdl-37494597

RESUMEN

The development of an array for high-throughput and logical analysis of biomarkers is significant for disease diagnosis. DNA-templated copper nanoclusters (CuNCs) have a strong potential to serve as a label-free photoluminescence source in array platforms, but their luminescent stability and sensitivity need to be improved. Herein, we report a facile, sensitive, and robust biomimetic array assay by integrating with stable luminescent CuNCs and entropy-driven nanomachine (EDN). In this strategy, the luminescent stability of CuNCs was improved by adding fructose in CuNCs synthesis to offer a reliable label-free signal. Meanwhile, the DNA template for CuNCs synthesis was introduced into EDN with excellent signal amplification ability, in which the reaction triggered by target miRNA would cause the blunt/protruding conformation change of 3'-terminus accompanied by the production or loss of luminescence. In addition, a biomimetic array fabricated by photonic crystals (PCs) physically enhanced the emitted luminescent signal of CuNCs and achieved high-throughput signal readout by a microplate reader. The proposed assay can isothermally detect as low as 4.5 pM of miR-21. Moreover, the logical EDN was constructed to achieve logical analysis of multiple miRNAs by "AND" or "OR" logic gate operation. Therefore, the proposed assay has the advantages of label-free property, high sensitivity, flexible design, and high-throughput analysis, which provides ideas for developing a new generation of facile and smart platforms in the fields of biological analysis and clinical application.


Asunto(s)
Nanopartículas del Metal , MicroARNs , Luminiscencia , ADN/química , Cobre/química , Biomimética , Entropía , MicroARNs/análisis , Nanopartículas del Metal/química , Espectrometría de Fluorescencia
19.
Anal Chem ; 95(2): 1599-1607, 2023 01 17.
Artículo en Inglés | MEDLINE | ID: mdl-36580626

RESUMEN

SARS-CoV-2, especially the variant strains, is rapidly spreading around the world. Rapid detection methods for the virus are crucial for controlling the COVID-19 epidemic. Herein, a localized surface plasmonic resonance (LSPR) biosensor based on Ω-shaped fiber optic (Ω-FO) was developed for dual assays of SARS-CoV-2 monitoring. Due to its strong ability to control the orientation and density, a new T-shaped aptamer exhibits enhanced binding affinity toward N proteins. After being combined on the fiber optic surface, the T-shaped aptamer sensitively captured N proteins of SARS-CoV-2 for a direct assay. Further, core-shell structured gold/silver nanoparticles functionalized with a T-shaped aptamer (apt-Ag@AuNPs) can amplify the signal of N protein detection for a sandwich assay. The real-time analytical feature of the dual assays endows time-dependent sensitivity enhancement behavior, which provides a guideline to save analytical time. With those characteristics, the LSPR biosensor has been successfully used to rapidly identify 39 healthy volunteers and 39 COVID-19 patients infected with the ancestral or variant SARS-CoV-2. With the help of simple pretreatment, we obtain a true negative rate of 100% and a true positive rate of 92.3% with a short analysis time of 45 min using the direct assay. Further, the LSPR biosensor could also broaden the detection application range to the surface of cold-chain foods using a sandwich assay. Thus, the LSPR biosensor based on Ω-FO was demonstrated to have broad application potential to detect SARS-CoV-2 rapidly.


Asunto(s)
Técnicas Biosensibles , COVID-19 , Nanopartículas del Metal , Humanos , Resonancia por Plasmón de Superficie/métodos , SARS-CoV-2 , Oro , COVID-19/diagnóstico , Plata , Técnicas Biosensibles/métodos , Oligonucleótidos
20.
Chemistry ; 29(45): e202300976, 2023 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-37221145

RESUMEN

Metal-Organic frameworks (MOFs) have the advantages of high porosity, angstrom-scale pore size, and unique structure. In this work, a kind of MOFs, UiO-66 and its derivatives (including aminated UiO-66-(NH2 )2 and sulfonated UiO-66-(NH-SAG)2 ), were constructed on the inner surface of solid-state nanopores for ultra-selective proton transport. UiO-66 and UiO-66-(NH2 )2 nanocrystal particles were in-situ grown at the orifice of glass nanopores firstly, which were used to investigate the ionic current responses in LiCl and HCl solutions when the monovalent anions (Cl- ) were unchanged. Compared with UiO-66-modifed nanopores, the aminated MOFs modification (UiO-66-(NH2 )2 ) can improve the proton selectivity obviously. However, when the UiO-66-(NH-SAG)2 nanopore is prepared by further post-modification with sulfo-acetic acid, lithium ions can hardly pass through the channel, and the interaction between protons and sulfonic acid groups can promote the transport of protons, thus achieving ultra-high selectivity to protons. This work provides a new way to achieve sub-nanochannels with high selectivity, which can widely be used in ion separation, sensing and energy conversion.

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