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Programmed DNA structures and assemblies are readily accessible, but site-specific functionalization is critical to realize applications in various fields such as nanoelectronics, nanomaterials and biomedicine. Besides pre- and post-DNA synthesis conjugation strategies, on-solid support reactions offer advantages in certain circumstances. We describe on-solid support internucleotide coupling reactions, often considered undesirable, and a workaround strategy to overcome them. Palladium coupling reactions enabled on-solid support intra- and interstrand coupling between single-stranded DNAs (ss-DNAs). Dilution with a capping agent suppressed interstrand coupling, maximizing intrastrand coupling. Alternatively, interstrand coupling actually proved advantageous to provide dimeric organic/DNA conjugates that could be conveniently separated from higher oligomers, and was more favorable with longer terphenyl coupling partners.
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Peptide IRW is the first food-derived angiotensin-converting enzyme 2 (ACE2) upregulator. This study aimed to investigate the pharmacokinetic characteristics of IRW and identify the metabolites contributing to its antihypertensive activity in spontaneously hypertensive rats (SHRs). Rats were administered 100 mg of IRW/kg of the body weight via an intragastric or intravenous route. The bioavailability (F %) was determined to be 11.7%, and the half-lives were 7.9 ± 0.5 and 28.5 ± 6.8 min for gavage and injection, respectively. Interestingly, significant blood pressure reduction was not observed until 1.5 h post oral administration, or 2 h post injection, indicating that the peptide's metabolites are likely responsible for the blood pressure-lowering activity. Time-course metabolomics revealed a significant increase in the level of kynurenine, a tryptophan metabolite, in blood after IRW administration. Kynurenine increased the level of ACE2 in cells. Oral administration of tryptophan (W), but not dipeptide IR, lowered the blood pressure and upregulated aortic ACE2 in SHRs. Our study supports the key role of tryptophan and its metabolite, kynurenine, in IRW's blood pressure-lowering effects.
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Enzima Convertidora de Angiotensina 2 , Hipertensión , Ratas , Animales , Ratas Endogámicas SHR , Enzima Convertidora de Angiotensina 2/metabolismo , Disponibilidad Biológica , Quinurenina/metabolismo , Quinurenina/farmacología , Triptófano/metabolismo , Péptidos/metabolismo , Antihipertensivos/farmacología , Presión Sanguínea , Hipertensión/metabolismo , Peptidil-Dipeptidasa A/metabolismoRESUMEN
Introduction: Perirenal fat is a pad that fills the retroperitoneal space outside the kidney, which affects kidney function in various ways. However, the association between perirenal fat and IgA nephropathy (IgAN) has not yet been elucidated. This study aimed to investigate the role of perirenal fat in predicting IgAN progression. Methods: A total of 473 patients with biopsy-proven IgAN and follow-up information were recruited, and perirenal fat thickness (PFT) was measured using color Doppler ultrasonography at renal biopsy. Patients were divided into two groups according to the median PFT: the low-PFT group (PFT ≤1.34 cm, n = 239) and the high PFT group (PFT >1.35 cm, n = 234). A total of 473 healthy participants were included in the control group. Basic clinical characteristics were assessed at the time of renal biopsy, and the relationship between PFT and combined endpoints was analyzed. The renal composite endpoints were defined as a two-fold increase in blood creatinine level, end-stage renal disease (dialysis over 3 months). Kaplan-Meier survival analysis was used to explore the role of PFT in the progression of IgAN. Three clinicopathological models of multivariate Cox regression analysis were established to evaluate the association between PFT and renal prognosis in patients with IgAN. Results: Compared to healthy subjects, patients with IgAN showed significantly higher PFT. After a median follow-up of 50 months, 75 of 473 patients (15.9%) with IgAN reached renal composite endpoints. Among those, 13 of 239 patients (5.4%) were in the low PFT group, and 62 of 234 patients (26.5%) were in the high PFT group (p < 0.001). The results of three Cox regression models (including demographics, pathological and clinical indicators, and PFT) demonstrated that a higher PFT was significantly associated with a higher risk of reaching renal composite endpoints in patients with IgAN. Conclusion: This study indicated a positive relationship between PFT at renal biopsy and renal progression in patients with IgAN, suggesting that perirenal fat might act as a marker of poor prognosis in patients with IgAN.
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BACKGROUND: Chemical isotope labeling (CIL) LC-MS is a powerful tool for metabolome analysis with high metabolomic coverage and quantification accuracy. In CIL LC-MS, the overall metabolite detection efficiency using Orbitrap MS can be further improved by employing a segment scan method where the full m/z range is divided into multiple segments for spectral acquisition with a significant increase in the in-spectrum dynamic range. Considering the metabolic complexity in different types of biological samples (e.g., feces, urine, serum/plasma, cell/tissue extracts, saliva, etc.), we report the development and evaluation of the segment scan method for metabolome analysis of different sample types. RESULTS: It was found that sample complexity significantly influenced the performance of the segment scan method. In metabolically complex samples such as feces and urine, the method yielded a substantial increase (up to 94 %) in detected peak pairs or metabolites, compared to conventional full scan. Conversely, less complex samples like saliva exhibited more modest gains (approximately 25 %). Based on the observations, a 120-m/z segment scan method was determined as a routine approach for CIL LC-Orbitrap-MS-based metabolomics with good compatibility with different types of biological samples. For this method, a further investigation on relative quantification accuracy was done. The peak area ratios of 12C-/13-labeled metabolites were slightly reduced with 72%-84 % of peak pairs falling within the ±25 % range of the anticipated peak ratio of 1.0 among different samples, as opposed to 81%-90 % in the full scan, which was attributed to the inclusion of more low-abundance peak pairs within the narrow MS segments. However, the overall peak ratio measurement precision was not significantly affected by the segment scan. SIGNIFICANCE AND NOVELTY: The segment scan method was found to be useful for CIL LC-Orbitrap-MS-based metabolome analysis of different types of samples with significant improvement in metabolite detectability (25-94 % increase), compared to the conventional full scan method.
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Cromatografía Líquida con Espectrometría de Masas , Espectrometría de Masas en Tándem , Cromatografía Liquida/métodos , Marcaje Isotópico/métodos , Compuestos de Dansilo , Metaboloma , Metabolómica/métodosRESUMEN
Holographic 3D display is highly desirable for numerous applications ranging from medical treatments to military affairs. However, it is challenging to simultaneously achieve large viewing angle and high-fidelity color reconstruction due to the intractable constraints of existing technology. Here, we conceptually propose and experimentally demonstrate a simple and feasible pathway of using a well-designed color liquid crystal grating to overcome the inevitable chromatic aberration and enlarge the holographic viewing angle, thus enabling large-viewing-angle and color holographic 3D display. The use of color liquid crystal grating allows performing secondary diffraction modulation on red, green and blue reproduced images simultaneously and extending the viewing angle in the holographic 3D display system. In principle, a chromatic aberration-free hologram generation mechanism in combination with the color liquid crystal grating is proposed to pave the way for on such a superior holographic 3D display. The proposed system shows a color viewing angle of ~50.12°, which is about 7 times that of the traditional system with a single spatial light modulator. This work presents a paradigm for achieving desirable holographic 3D display, and is expected to provide a new way for the wide application of holographic display.
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Solar-energy-driven CO2 hydrogenation is a promising strategy to alleviate the climate crisis. Methane is a desirable derivative of CO2 reduction. However, developing a photocatalyst for highly active and selective CH4 generation remains challenging. Herein, we report a double Z-scheme Bi3O4Cl/g-C3N4/Cd0.5Zn0.5S photocatalyst for efficient reduction of CO2 to CH4. In situ characterization techniques confirmed that the charge migration mechanism in Bi3O4Cl/g-C3N4/Cd0.5Zn0.5S promotes charge separation through double internal electric fields. As a result, the optimized C0.01B0.02C catalyst displayed a formation rate high up to 25.34 µmol g-1 h-1 and a selectivity of 96.52% of CH4. Moreover, the AQY of CO2 conversion on C0.01B0.02C (1.84%) was almost 41 times higher than that of the bare CN. This study provides a novel perspective to develop heterojunction photocatalysts for selective CO2 conversion to CH4.
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The next-generation diffraction grating not only requires a nonmechanical control and a remote control to generate a diffraction pattern but also requires a tunable period. Here, we propose a stimuli-responsive liquid crystal (LC) phase grating with a tunable period and a diffraction order. The stimuli-responsive LC diffraction grating is composed of periodically arranged electrodes on a double-sided glass substrate. By adjusting the driving scheme, the pitch and diffraction order of the LC grating can be switched between three different modes. The experimental results show that the LC grating has a lower driving voltage (â¼5â V). In addition, the tunable LC grating can achieve more diffraction orders, which can be applied to a holographic display to achieve a wide-viewing angle and an enlarged size.
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[This corrects the article DOI: 10.3389/fnins.2022.972288.].
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In this research, a ternary Cu-CuTCPP/Cu2O/CoAl-LDH composite with a dual Z-scheme heterostructure was fabricated based on a Cu2O photocatalyst and applied in photocatalytic CO2 reduction. The physicochemical properties of the prepared catalysts and the possible reaction mechanism in CO2 reduction were analyzed and studied by various characterization methods. The activity of CO2 reduction significantly increased, especially forming C2 products. The optimal yield of C2H4 and C2H6 reached 1.56 and 1.92 µmol g-1 h-1 respectively, which was 14.45 and 17.45 times that from using the Cu2O monomer. In addition, the selectivity of C2 products reached 37.4%. The satisfactory C2 yield was mainly due to the fact that Cu1+δ2(COO)3 nodes in Cu-CuTCPP contained adjacent Cu sites, which effectively promoted the C-C coupling reaction. Moreover, the dual Z-scheme heterojunction stimulated the separation of photogenerated electron-hole pairs and diminished the recombination rate. This work contributes to the development of novel photocatalysts with a dual Z-scheme heterojunction and facilitates the generation of valuable C2 products.
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Covalent organic frameworks (COFs) are one type of porous organic materials linked by covalent bonds. COFs materials exhibit many outstanding characteristics such as high porosity, high chemical and thermal stability, large specific surface area, efficient electron transfer efficiency, and the ability for predesigned structures. These exceptional advantages enable COFs materials to exhibit remarkable performance in photocatalysis. Additionally, the activity of COFs materials as photocatalysts can be significantly upgraded by ion doping and the formation of heterojunctions. This paper summarizes the latest research progress on COF-based materials applied in photocatalytic systems. Initially, typical structures and preparation methods of COFs are analyzed and compared. Moreover, the essential principles of photocatalytic reactions over COFs-based materials and the latest research developments in photocatalytic hydrogen production, CO2 reduction, pollutants elimination, organic transformation, and overall water splitting are indicated. At last, the outlook and challenges of COF-based materials in photocatalysis are discussed. This review is intended to permit instructive guidance for the efficient use of photocatalysis based on COFs in the future.
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Metal-mediated DNA (mmDNA) presents a pathway toward engineering bioinorganic and electronic behavior into DNA devices. Many chemical and biophysical forces drive the programmable chelation of metals between pyrimidine base pairs. Here, we developed a crystallographic method using the three-dimensional (3D) DNA tensegrity triangle motif to capture single- and multi-metal binding modes across granular changes to environmental pH using anomalous scattering. Leveraging this programmable crystal, we determined 28 biomolecular structures to capture mmDNA reactions. We found that silver(I) binds with increasing occupancy in T-T and U-U pairs at elevated pH levels, and we exploited this to capture silver(I) and mercury(II) within the same base pair and to isolate the titration points for homo- and heterometal base pair modes. We additionally determined the structure of a C-C pair with both silver(I) and mercury(II). Finally, we extend our paradigm to capture cadmium(II) in T-T pairs together with mercury(II) at high pH. The precision self-assembly of heterobimetallic DNA chemistry at the sub-nanometer scale will enable atomistic design frameworks for more elaborate mmDNA-based nanodevices and nanotechnologies.
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Mercurio , Plata , Emparejamiento Base , Plata/química , ADN/química , Mercurio/químicaRESUMEN
Converting CO2 into chemicals and fuels by solar energy can alleviate global warming and solve the energy crisis. In this work, CoAl-LDO/MoO3-x (LDO/MO) composites were successfully prepared and achieved efficient CO2 reduction under visible light. The CoAl-layered double oxides (CoAl-LDO) evolved from CoAl-layered double hydroxide (CoAl-LDH) exhibited a more robust structure, broader light absorption, and improved CO2 adsorption ability. The local surface plasmon resonance (LSPR) effect excited by nonstoichiometric MoO3-x broadened the photo-response range of CoAl-LDO/MoO3-x. In addition, constructing step-scheme (S-scheme) heterojunctions could simultaneously optimize the migration mechanism of photogenerated electrons and holes, and retain carriers with strong redox ability. Therefore, the production rates of CO and CH4 on the optimal LDO/MO composite were 7 and 9 times higher than the pristine CoAl-LDH, respectively. This work hybridizes oxidation photocatalysts and LDO-based materials to optimize the charge separation and migration mechanisms, which guides the modification of LDO-based materials.
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DNA double helices containing metal-mediated DNA (mmDNA) base pairs are constructed from Ag+ and Hg2+ ions between pyrimidine:pyrimidine pairs with the promise of nanoelectronics. Rational design of mmDNA nanomaterials is impractical without a complete lexical and structural description. Here, the programmability of structural DNA nanotechnology toward its founding mission of self-assembling a diffraction platform for biomolecular structure determination is explored. The tensegrity triangle is employed to build a comprehensive structural library of mmDNA pairs via X-ray diffraction and generalized design rules for mmDNA construction are elucidated. Two binding modes are uncovered: N3-dominant, centrosymmetric pairs and major groove binders driven by 5-position ring modifications. Energy gap calculations show additional levels in the lowest unoccupied molecular orbitals (LUMO) of mmDNA structures, rendering them attractive molecular electronic candidates.
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ADN , Metales , Metales/química , ADN/química , Emparejamiento Base , Pirimidinas/química , Nanotecnología , Conformación de Ácido NucleicoRESUMEN
Ammonia selective catalytic reduction (NH3-SCR) of nitrogen oxides is an effective and well-established technology for NOx removal, but current commercial denitrification catalysts based on V2O5-WO3/TiO2 have some obvious disadvantages, including narrow operating temperature windows, toxicity, poor hydrothermal stability, and unsatisfied SO2/H2O tolerance. To overcome these drawbacks, it is imperative to investigate new types of highly efficient catalysts. In order to design catalysts with outstanding selectivity, activity, and anti-poisoning ability, core-shell structured materials have been widely applied in the NH3-SCR reaction, which exhibits numerous advantages including the large surface area, the strong synergy interaction of core-shell materials, the confinement effect, and the shielding effect from the shell layer to protect the core. This review summarizes recent developments of core-shell structured catalysts for NH3-SCR, including basic classification, synthesis methods, and a detailed description of the performance and mechanisms of each type of catalyst. It is hoped that the review will stimulate future developments in NH3-SCR technology, leading to novel catalyst designs with improved denitrification performance.
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Amoníaco , Titanio , Temperatura , Frío , Óxidos de Nitrógeno , Catálisis , Oxidación-ReducciónRESUMEN
Photocatalytic CO2 reduction to valuable fuels is a promising way to alleviate anthropogenic CO2 emissions and energy crises. Perovskite oxides have attracted widespread attention as photocatalysts for CO2 reduction by virtue of their high catalytic activity, compositional flexibility, bandgap adjustability, and good stability. In this review, the basic theory of photocatalysis and the mechanism of CO2 reduction over perovskite oxide are first introduced. Then, perovskite oxides' structures, properties, and preparations are presented. In detail, the research progress on perovskite oxides for photocatalytic CO2 reduction is discussed from five aspects: as a photocatalyst in its own right, metal cation doping at A and B sites of perovskite oxides, anion doping at O sites of perovskite oxides and oxygen vacancies, loading cocatalyst on perovskite oxides, and constructing heterojunction with other semiconductors. Finally, the development prospects of perovskite oxides for photocatalytic CO2 reduction are put forward. This article should serve as a useful guide for creating perovskite oxide-based photocatalysts that are more effective and reasonable.
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A photocatalytic system driven by solar light is one of the promising strategies for converting CO2 into valuable energy. The reduction of CO2 to CH4 is widely studied since CH4 has a high energy density as the main component of nonrenewable natural gas. Therefore, it is necessary to develop semiconductor materials with high photocatalytic activity and CH4 selectivity. Graphitic carbon nitride (g-C3N4/CN) has attracted widespread attention for photocatalytic CO2 reduction due to its excellent redox ability and visible light response. A hybrid system constructed by loading cocatalysts on g-C3N4 can significantly improve the yield of target products, and serve as a general platform to explore the mechanism of the CO2 reduction reaction. Herein, we briefly introduce the theory of selective CO2 photoreduction and the basic properties of cocatalysts. Then, several typical configurations and modification strategies of cocatalyst/CN systems for promoting CH4 selective production are presented in detail. In particular, we systematically summarize the application of cocatalyst/CN composite photocatalysts in the selective reduction of CO2 to methane, according to the classification of cocatalysts (monometal, bimetal, metal-based compound, and nanocarbon materials). Finally, the challenges and perspectives for developing cocatalyst/g-C3N4 systems with high CH4 selectivity are presented to guide the rational design of catalysts with high performance in the future.
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The photocatalytic reduction of CO2 to hydrocarbons is expected to simultaneously alleviate the energy crisis and greenhouse effect. Herein, the ternary BiOCl/C/Cu2O catalysts with different mass ratios were compounded using a simple hydrothermal method, revealing better photocatalytic activity than the monomer. In the absence of sacrificial agents and photosensitizers, 25% BiOCl/C/Cu2O showed optimal photocatalytic performance. The CO and CH4 yields over 25% BiOCl/C/Cu2O reached 26.77 and 9.86 µmol g-1 h-1, which is 2.9 and 8.7 times higher than that of the pristine Cu2O, respectively. The ameliorative activity can be attributed to the construction of the Z-scheme heterostructure and carbon layer, which are conducive to the transfer and separation of photogenerated carriers. This study offers valuable references for the design and investigation of a Z-scheme heterojunction using a carbon layer as an electron transfer medium.
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DNA double helices containing metal-mediated DNA (mmDNA) base pairs have been constructed from Ag+ and Hg2+ ions between pyrimidine:pyrimidine pairs with the promise of nanoelectronics. Rational design of mmDNA nanomaterials has been impractical without a complete lexical and structural description. Here, we explore the programmability of structural DNA nanotechnology toward its founding mission of self-assembling a diffraction platform for biomolecular structure determination. We employed the tensegrity triangle to build a comprehensive structural library of mmDNA pairs via X-ray diffraction and elucidated generalized design rules for mmDNA construction. We uncovered two binding modes: N3-dominant, centrosymmetric pairs and major groove binders driven by 5-position ring modifications. Energy gap calculations showed additional levels in the lowest unoccupied molecular orbitals (LUMO) of mmDNA structures, rendering them attractive molecular electronic candidates. This article is protected by copyright. All rights reserved.