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1.
Liver Int ; 2024 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-38963299

RESUMO

BACKGROUND AND AIMS: Lifestyle intervention is the mainstay of therapy for metabolic dysfunction-associated steatohepatitis (MASH), and liver fibrosis is a key consequence of MASH that predicts adverse clinical outcomes. The placebo response plays a pivotal role in the outcome of MASH clinical trials. Second harmonic generation/two-photon excitation fluorescence (SHG/TPEF) microscopy with artificial intelligence analyses can provide an automated quantitative assessment of fibrosis features on a continuous scale called qFibrosis. In this exploratory study, we used this approach to gain insight into the effect of lifestyle intervention-induced fibrosis changes in MASH. METHODS: We examined unstained sections from paired liver biopsies (baseline and end-of-intervention) from MASH individuals who had received either routine lifestyle intervention (RLI) (n = 35) or strengthened lifestyle intervention (SLI) (n = 17). We quantified liver fibrosis with qFibrosis in the portal tract, periportal, transitional, pericentral, and central vein regions. RESULTS: About 20% (7/35) and 65% (11/17) of patients had fibrosis regression in the RLI and SLI groups, respectively. Liver fibrosis tended towards no change or regression after each lifestyle intervention, and this phenomenon was more prominent in the SLI group. SLI-induced liver fibrosis regression was concentrated in the periportal region. CONCLUSION: Using digital pathology, we could detect a more pronounced fibrosis regression with SLI, mainly in the periportal region. With changes in fibrosis area in the periportal region, we could differentiate RLI and SLI patients in the placebo group in the MASH clinical trial. Digital pathology provides new insight into lifestyle-induced fibrosis regression and placebo responses, which is not captured by conventional histological staging.

2.
Liver Int ; 2024 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-38847599

RESUMO

BACKGROUND AND AIMS: Metabolic dysfunction-associated steatotic liver disease (MASLD) represents the foremost cause of chronic liver disease, yet its underlying mechanisms remain elusive. Our group previously discovered a novel long non-coding RNA (lncRNA) in rats, termed lncHC and its human counterpart, LNCHC. This study aimed to explore the role of LNCHC in the progression of MASLD. METHODS: RNA-binding proteins bound to LNCHC were searched by mass spectrometry. The target genes of LNCHC and Y-Box binding protein 1 (YBX1) were identified by RNA-seq. MASLD animal models were utilised to examine the roles of LNCHC, YBX1 and patatin-like phospholipase domain containing 3 (PNPLA3) in MASLD progression. RESULTS: Here, we identified LNCHC as a native restrainer during MASLD development. Notably, LNCHC directly binds YBX1 and prevents protein ubiquitination. Up-regulation of YBX1 then stabilises PNPLA3 mRNA to alleviate lipid accumulation in hepatocytes. Furthermore, both cell and animal studies demonstrate that LNCHC, YBX1 and PNPLA3 function to improve hepatocyte lipid accumulation and exacerbate metabolic dysfunction-associated steatohepatitis development. CONCLUSIONS: In summary, our findings unveil a novel LNCHC functionality in regulating YBX1 and PNPLA3 mRNA stability during MASLD development, providing new avenues in MASLD treatment.

3.
Nat Commun ; 15(1): 2390, 2024 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-38493199

RESUMO

Metal-halide perovskite thin monocrystals featuring efficient carrier collection and transport capabilities are well suited for radiation detectors, yet their growth in a generic, well-controlled manner remains challenging. Here, we reveal that mass transfer is one major limiting factor during solution growth of perovskite thin monocrystals. A general approach is developed to overcome synthetic limitation by using a high solute flux system, in which mass diffusion coefficient is improved from 1.7×10-10 to 5.4×10-10 m2 s-1 by suppressing monomer aggregation. The generality of this approach is validated by the synthesis of 29 types of perovskite thin monocrystals at 40-90 °C with the growth velocity up to 27.2 µm min-1. The as-grown perovskite monocrystals deliver a high X-ray sensitivity of 1.74×105 µC Gy-1 cm-2 without applied bias. The findings regarding limited mass transfer and high-flux crystallization are crucial towards advancing the preparation and application of perovskite thin monocrystals.

4.
J Am Chem Soc ; 146(6): 3764-3772, 2024 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-38304977

RESUMO

TiO2-supported Pt species have been widely applied in numerous critical reactions involving photo-, thermo-, and electrochemical-catalysis for decades. Manipulation of the state of the Pt species in Pt/TiO2 catalysts is crucial for fine-tuning their catalytic performance. Here, we report an interesting discovery showing the epitaxial growth of PtO2 atomic layers on rutile TiO2, potentially allowing control of the states of active Pt species in Pt/TiO2 catalysts. The presence of PtO2 atomic layers could modulate the geometric configuration and electronic state of the Pt species under reduction conditions, resulting in a spread of the particle shape and obtaining a Pt/PtO2/TiO2 structure with more positive valence of Pt species. As a result, such a catalyst exhibits exceptional electrocatalytic activity and stability toward hydrogen evolution reaction, while also promoting the thermocatalytic CO oxidation, surpassing the performance of the Pt/TiO2 catalyst with no epitaxial structure. This novel epitaxial growth of the PtO2 structure on rutile TiO2 in Pt/TiO2 catalysts shows its potential in the rational design of highly active and economical catalysts toward diverse catalytic reactions.

5.
Adv Mater ; 36(6): e2307855, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37897435

RESUMO

Perovskite solar cells (PSCs) are promising candidates for next-generation photovoltaics owing to their unparalleled power conversion efficiencies (PCEs). Currently, approaches to further improve device efficiencies tend to focus on the passivation of interfacial defects. Although various strategies have been developed to mitigate these defects, many involve complex and time-consuming post-treatment processes, thereby hindering their widespread adoption in commercial applications. In this work, a concise but efficient in situ dual-interface passivation strategy is developed wherein 1-butyl-3-methylimidazolium methanesulfonate (MS) is employed as a precursor additive. During perovskite crystallization, MS can either be enriched downward through precipitation with SnO2 , or can be aggregated upward through lattice extrusion. These self-assembled MS species play a significant role in passivating the defect interfaces, thereby reducing nonradiative recombination losses, and promoting more efficient charge extraction. As a result, a PCE >25% (certified PCE of 24.84%) is achieved with substantially improved long-term storage and photothermal stabilities. This strategy provides valuable insights into interfacial passivation and holds promise for the industrialization of PSCs.

6.
J Shoulder Elbow Surg ; 33(5): 1138-1149, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-37944743

RESUMO

BACKGROUND: Distal humerus fractures are a challenge to treat, and the current standard of care, open reduction internal fixation with a double-plate, has a high rate of complications. We proposed a novel internal fixation configuration, lateral intramedullary nail and medial plate (LINMP) and verified its rigidity through biomechanical tests and finite element analysis. METHODS: The study involved biomechanical testing of 30 synthetic humerus models to compare 2 different fixation systems for an AO 13C-2.3 type fracture. The orthogonal double-plate (ODP) group and the LINMP group were compared through biomechanical testing to measure stiffness and failure load fewer than 3 working conditions. Based on the results, we optimized the intramedullary nail by eliminating the holes at the distal end of the nail and incorporating a 2-hole external locking plate. The Finite element analysis was also conducted to further compare the modified LINMP configuration with the previous 2 fixation configurations. RESULTS: In biomechanical tests, the ODP group exhibited lower stiffness under bending and compression forces compared to the LINMP group, but higher stiffness and failure loads under torsion force. In finite element analysis, the modified LINMP reduces the maximum stress of the fixation structure without significantly reducing the stiffness under bending stress and axial compression conditions. In torsion stress conditions, the modified LINMP enhances both the maximum stress and the stiffness, although it remains marginally inferior to the ODP structure. CONCLUSION: Our study demonstrates that the innovative LINMP presents comparable or slightly superior concerning bending and axial loading compared to orthogonal double-plate osteosynthesis for distal humeral intra-articular fractures, which might become a minimally invasive option for these fractures.


Assuntos
Fraturas Distais do Úmero , Fraturas do Úmero , Humanos , Fraturas do Úmero/cirurgia , Análise de Elementos Finitos , Fenômenos Biomecânicos , Úmero/cirurgia , Fixação Interna de Fraturas/métodos , Placas Ósseas , Procedimentos Cirúrgicos Minimamente Invasivos
7.
Cell Metab ; 35(12): 2231-2249.e7, 2023 12 05.
Artigo em Inglês | MEDLINE | ID: mdl-38056431

RESUMO

Metabolic dysfunction-associated steatohepatitis (MASH) is a leading risk factor for liver cirrhosis and hepatocellular carcinoma. Here, we report that CHRNA4, a subunit of nicotinic acetylcholine receptors (nAChRs), is an accelerator of MASH progression. CHRNA4 also mediates the MASH-promotive effects induced by smoking. Chrna4 was expressed specifically in hepatocytes and exhibited increased levels in mice and patients with MASH. Elevated CHRNA4 levels were positively correlated with MASH severity. We further revealed that during MASH development, acetylcholine released from immune cells or nicotine derived from smoking functioned as an agonist to activate hepatocyte-intrinsic CHRNA4, inducing calcium influx and activation of inflammatory signaling. The communication between immune cells and hepatocytes via the acetylcholine-CHRNA4 axis led to the production of a variety of cytokines, eliciting inflammation in liver and promoting the pathogenesis of MASH. Genetic and pharmacological inhibition of CHRNA4 protected mice from diet-induced MASH. Targeting CHRNA4 might be a promising strategy for MASH therapeutics.


Assuntos
Acetilcolina , Fígado Gorduroso , Humanos , Animais , Camundongos , Polimorfismo de Nucleotídeo Único , Fumar/efeitos adversos , Fumar/genética , Hepatócitos
8.
Nano Lett ; 23(23): 11314-11322, 2023 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-38018816

RESUMO

The electrochemical 5-hydroxymethylfurfural oxidation reaction (HMFOR) has been regarded as a viable alternative to sustainable biomass valorization. However, the transformation of the catalysts under harsh electrooxidation conditions remains controversial. Herein, we confirm the self-construction of cuprous sulfide nanosheets (Cu2S NSs) into sulfate-terminated copper oxide nanorods (CuO-SO42- NRs) during the first-cycle of the HMFOR, which achieves a near-quantitative synthesis of 2,5-furandicarboxylic acid (FDCA) with a >99.9% yield and faradaic efficiency without deactivation in 15 successive cycles. Electrochemical impedance spectroscopies confirm that the surface SO42- effectively reduces the onset potential for HMFOR, while in situ Raman spectroscopies identify a reversible transformation from CuII-O to CuIII-OOH in HMFOR. Furthermore, density functional theory calculations reveal that the surface SO42- weakens the Cu-OH bonds in CuOOH to promote the rate-determining step of its coupling with the C atom in HMF-H* resulting from HMF hydrogenation, which synergistically enhances the catalytic activity of CuO-SO42- NRs toward HMF-to-FDCA conversion.

9.
Aliment Pharmacol Ther ; 58(6): 573-584, 2023 09.
Artigo em Inglês | MEDLINE | ID: mdl-37403450

RESUMO

BACKGROUND: Liver fibrosis is the strongest histological risk factor for liver-related complications and mortality in metabolic dysfunction-associated fatty liver disease (MAFLD). Second harmonic generation/two-photon excitation fluorescence (SHG/TPEF) is a powerful tool for label-free two-dimensional and three-dimensional tissue visualisation that shows promise in liver fibrosis assessment. AIM: To investigate combining multi-photon microscopy (MPM) and deep learning techniques to develop and validate a new automated quantitative histological classification tool, named AutoFibroNet (Automated Liver Fibrosis Grading Network), for accurately staging liver fibrosis in MAFLD. METHODS: AutoFibroNet was developed in a training cohort that consisted of 203 Chinese adults with biopsy-confirmed MAFLD. Three deep learning models (VGG16, ResNet34, and MobileNet V3) were used to train pre-processed images and test data sets. Multi-layer perceptrons were used to fuse data (deep learning features, clinical features, and manual features) to build a joint model. This model was then validated in two further independent cohorts. RESULTS: AutoFibroNet showed good discrimination in the training set. For F0, F1, F2 and F3-4 fibrosis stages, the area under the receiver operating characteristic curves (AUROC) of AutoFibroNet were 1.00, 0.99, 0.98 and 0.98. The AUROCs of F0, F1, F2 and F3-4 fibrosis stages for AutoFibroNet in the two validation cohorts were 0.99, 0.83, 0.80 and 0.90 and 1.00, 0.83, 0.80 and 0.94, respectively, showing a good discriminatory ability in different cohorts. CONCLUSION: AutoFibroNet is an automated quantitative tool that accurately identifies histological stages of liver fibrosis in Chinese individuals with MAFLD.


Assuntos
Aprendizado Profundo , Hepatopatia Gordurosa não Alcoólica , Adulto , Humanos , Microscopia , Cirrose Hepática/diagnóstico , Cirrose Hepática/patologia , Fígado/patologia , Hepatopatia Gordurosa não Alcoólica/patologia , Biópsia
10.
Liver Int ; 43(6): 1234-1246, 2023 06.
Artigo em Inglês | MEDLINE | ID: mdl-36924436

RESUMO

BACKGROUND & AIMS: There is an unmet clinical need for non-invasive tests to diagnose non-alcoholic fatty liver disease (NAFLD) and individual fibrosis stages. We aimed to test whether urine protein panels could be used to identify NAFLD, NAFLD with fibrosis (stage F ≥ 1) and NAFLD with significant fibrosis (stage F ≥ 2). METHODS: We collected urine samples from 100 patients with biopsy-confirmed NAFLD and 40 healthy volunteers, and proteomics and bioinformatics analyses were performed in this derivation cohort. Diagnostic models were developed for detecting NAFLD (UPNAFLD model), NAFLD with fibrosis (UPfibrosis model), or NAFLD with significant fibrosis (UPsignificant fibrosis model). Subsequently, the derivation cohort was divided into training and testing sets to evaluate the efficacy of these diagnostic models. Finally, in a separate independent validation cohort of 100 patients with biopsy-confirmed NAFLD and 45 healthy controls, urinary enzyme-linked immunosorbent assay analyses were undertaken to validate the accuracy of these new diagnostic models. RESULTS: The UPfibrosis model and the UPsignificant fibrosis model showed an AUROC of .863 (95% CI: .725-1.000) and 0.858 (95% CI: .712-1.000) in the training set; and .837 (95% CI: .711-.963) and .916 (95% CI: .825-1.000) in the testing set respectively. The UPNAFLD model showed an excellent diagnostic performance and the area under the receiver operator characteristic curve (AUROC) exceeded .90 in the derivation cohort. In the independent validation cohort, the AUROC for all three of the above diagnostic models exceeded .80. CONCLUSIONS: Our newly developed models constructed from urine protein biomarkers have good accuracy for non-invasively diagnosing liver fibrosis in NAFLD.


Assuntos
Hepatopatia Gordurosa não Alcoólica , Humanos , Hepatopatia Gordurosa não Alcoólica/patologia , Cirrose Hepática/patologia , Fibrose , Biomarcadores/metabolismo , Biópsia , Fígado/patologia
11.
Hepatol Int ; 17(1): 190-201, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36152131

RESUMO

BACKGROUND AND AIMS: With metabolic dysfunction-associated fatty liver disease (MAFLD) incidence and prevalence sharply increasing globally, there is an urgent need for non-invasive diagnostic tests to accurately screen high-risk MAFLD patients for liver inflammation and fibrosis. We aimed to develop a novel sequential algorithm based on N-terminal propeptide of type 3 collagen (PRO-C3) for disease risk stratification in patients with MAFLD. METHODS: A derivation and independent validation cohort of 327 and 142 patients with biopsy-confirmed MAFLD were studied. We compared the diagnostic performances of various non-invasive scores in different disease states, and a novel sequential algorithm was constructed by combining the best performing non-invasive scores. RESULTS: For patients with high-risk progressive steatohepatitis (i.e., steatohepatitis + NAFLD activity score ≥ 4 + F ≥ 2), the AUROC of FAST score was 0.801 (95% confidence interval (CI): 0.739-0.863), and the negative predictive value (NPV) was 0.951. For advanced fibrosis (≥ F3) and cirrhosis (F4), the AUROCs of ADAPT and Agile 4 were 0.879 (95%CI 0.825-0.933) and 0.943 (95%CI 0.892-0.994), and the NPV were 0.972 and 0.992. Sequential algorithm of ADAPT + Agile 4 combination was better than other combinations for risk stratification of patients with severe fibrosis (AUROC = 0.88), with similar results in the validation cohort. Meanwhile, in all subgroup analyses (stratifying by sex, age, diabetes, NAS, BMI and ALT), ADAPT + Agile 4 had a good diagnostic performance. CONCLUSIONS: The new sequential algorithm reliably identifies liver inflammation and fibrosis in MAFLD, making it easier to exclude low-risk patients and recommending high-risk MAFLD patients for clinical trials and emerging pharmacotherapies.


Assuntos
Hepatopatia Gordurosa não Alcoólica , Humanos , Hepatopatia Gordurosa não Alcoólica/complicações , Hepatopatia Gordurosa não Alcoólica/diagnóstico , Fibrose , Cirrose Hepática/complicações , Algoritmos , Colágeno
12.
Angew Chem Int Ed Engl ; 61(52): e202212703, 2022 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-36321806

RESUMO

Effective adsorption and speedy surface reactions are vital requirements for efficient active sites in catalysis, but it remains challenging to maximize these two functions simultaneously. We present a solution to this issue by designing a series of atom-pair catalytic sites with tunable electronic interactions. As a case study, NO selective reduction occurring on V1 -W1 /TiO2 is chosen. Experimental and theoretical results reveal that the synergistic electron effect present between the paired atoms enriches high-energy spin charge around the Fermi level, simultaneously rendering reactant (NH3 or O2 ) adsorption more effective and subsequent surface reactions speedier as compared with single V or W atom alone, and hence higher reaction rates. This strategy enables us to rationally design a high-performance V1 -Mo1 /TiO2 catalyst with optimized vanadium(IV)-molybdenum(V) electronic interactions, which has exceptional activity significantly higher than the commercial or reported catalysts.

13.
ChemSusChem ; 15(23): e202201394, 2022 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-36116112

RESUMO

Inorganic perovskite solar cells have attracted wide attention due to their excellent thermodynamic stability and suitable bandgap as the top absorber materials for tandem solar cells. However, the power conversion efficiencies (PCEs) of the perovskite cells can be considerably limited by the non-radiative energy loss caused by grain boundaries and surfaces. Here, the synergistic functionalization of CsPbI2 Br perovskites was demonstrated by using a metal-organic complex. Experimental and theoretical studies revealed that the adsorption energy of the passivator could be a good descriptor to evaluate the surface passivation effect. The cooperative adsorption could eliminate the unsaturated surface sites, reduce the surface energy, and thus benefit device performance. The CsPbI2 Br solar cells passivated by zinc diethyldithiocarbamate showed a champion power conversion efficiency of 17.15 % and retained 94 % of their initial efficiency after working under 1 sun illumination for 720 h in N2 atmosphere.

14.
Hepatol Int ; 16(5): 1085-1093, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-35829867

RESUMO

BACKGROUND/PURPOSE OF THE STUDY: Although low skeletal muscle mass is associated with non-alcoholic fatty liver disease (NAFLD), it is currently uncertain whether there are associations between weight-adjusted appendicular skeletal muscle (ASM%), severity of histological features of NAFLD, and the patatin-like phospholipase domain-containing 3 (PNPLA3) rs738409 polymorphism. Our aim was to test for a possible influence of the PNPLA3 rs738409 variant on the association between ASM% and severity of NAFLD histological features. METHODS: We enrolled 401 Chinese male with biopsy-proven NAFLD. Using a bioelectrical-impedance body composition analyzer (BIA, Inbody 720, Japan Inc., Tokyo), we calculated the ASM% as the percentage of total appendicular skeletal muscle mass (ASM, kg)/total body mass (kg) × 100. RESULTS: Compared to those with high ASM%, patients with low ASM% (≤ 30.6, i.e., the median value of distribution of the whole sample) had a greater severity of individual histological features of NAFLD. These patients also had a higher risk of severe steatosis and non-alcoholic steatohepatitis (NASH) (adjusted-odds ratio [OR] 2.34, 95% CI 1.39-3.93, and adjusted-OR 2.22, 95% CI 1.30-3.77) even after adjusting for age, body mass index, diabetes, and serum creatinine levels. Carriage of the G allele of PNPLA3 rs738409 plus low ASM% was associated with a higher risk of severe steatosis and presence of liver fibrosis (OR 3.02, 95% CI 1.46-6.26, p = 0.003 and OR 2.18, 95% CI 1.03-4.60, p = 0.041 respectively), and there was a non-significant but borderline increased risk of NASH (OR 2.00, 95% CI 0.98-4.06, p = 0.056). CONCLUSIONS: Low ASM% and the presence of a G allele within PNPLA3 rs738409 is associated with more severe histological features of NAFLD.


Assuntos
Hepatopatia Gordurosa não Alcoólica , Creatinina , Predisposição Genética para Doença , Humanos , Lipase/genética , Fígado/patologia , Masculino , Proteínas de Membrana/genética , Músculo Esquelético , Hepatopatia Gordurosa não Alcoólica/patologia , Fosfolipases , Polimorfismo de Nucleotídeo Único
15.
J Gastroenterol Hepatol ; 37(11): 2145-2153, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-35816347

RESUMO

BACKGROUND AND AIM: Over 10% of hepatocellular carcinoma (HCC) cases recur each year, even after surgical resection. Currently, there is a lack of knowledge about the causes of recurrence and the effective prevention. Prediction of HCC recurrence requires diagnostic markers endowed with high sensitivity and specificity. This study aims to identify new key proteins for HCC recurrence and to build machine learning algorithms for predicting HCC recurrence. METHODS: The proteomics data for analysis in this study were obtained from the Clinical Proteomics Tumor Analysis Consortium (CPTAC) database. We analyzed different proteins based on cases with or without recurrence of HCC. Survival analysis, Cox regression analysis, and area under the ROC curves (AUROC > 0.7) were used to screen for more significant differential proteins. Predictive models for HCC recurrence were developed using four machine learning algorithms. RESULTS: A total of 690 differentially expressed proteins between 50 relapsed and 77 non-relapsed hepatitis B-related HCC patients were identified. Seven of these proteins had an AUROC > 0.7 for 5-year survival in HCC, including BAHCC1, ESF1, RAP1GAP, RUFY1, SCAMP3, STK3, and TMEM230. Among the machine learning algorithms, the random forest algorithm showed the highest AUROC values (AUROC: 0.991, 95% CI 0.962-0.999) for identifying HCC recurrence, followed by the support vector machine (AUROC: 0.893, 95% Cl 0.824-0.956), the logistic regression (AUROC: 0.774, 95% Cl 0.672-0.868), and the multi-layer perceptron algorithm (AUROC: 0.571, 95% Cl 0.459-0.682). CONCLUSIONS: Our study identifies seven novel proteins for predicting HCC recurrence and the random forest algorithm as the most suitable predictive model for HCC recurrence.


Assuntos
Carcinoma Hepatocelular , Hepatite B , Neoplasias Hepáticas , Doença de Parkinson , Humanos , Carcinoma Hepatocelular/diagnóstico , Carcinoma Hepatocelular/cirurgia , Carcinoma Hepatocelular/patologia , Neoplasias Hepáticas/cirurgia , Neoplasias Hepáticas/patologia , Proteômica , Proteínas de Membrana , Algoritmos , Aprendizado de Máquina , Mineração de Dados , Proteínas Serina-Treonina Quinases , Proteínas de Transporte
16.
Langmuir ; 38(26): 8179-8186, 2022 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-35748635

RESUMO

In this work, we have investigated a pH-modulated complexation between two oppositely charged strong polyelectrolytes to demonstrate the effect of counterion-mediated hydrogen bonding (CMHB) on polyelectrolyte complexation. We have found that such a pH-modulated complexation cannot be understood without considering the CMHB. Thermodynamically, the effect of CMHB on the polyelectrolyte complexation is manifested by the alteration of both enthalpic and entropic contributions to the free energy change. The pH-dependent intrinsic ion-pairing and complex coacervation processes of the polyelectrolyte complexation can be understood when considering the CMHB. Our study demonstrates that both the extent of polyelectrolyte complex formation in bulk solutions and the formation of polyelectrolyte multilayers on surfaces are controlled by the pH-dependent intrinsic ion-pairing process. Furthermore, on the basis of the pH-dependent intrinsic ion pairing, the properties of the multilayers can be tuned by pH. This work provides a new strategy to control the polyelectrolyte complexation with counterions and will inspire new ideas for building advanced polyelectrolyte materials.

17.
Langmuir ; 38(19): 6164-6173, 2022 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-35512818

RESUMO

Surface force measurements have revealed that at very high electrolyte concentrations as well as in neat and diluted ionic liquids and deep eutectic solvents, the range of electrostatic interactions is far greater than the Debye length. Here, we explore the consequences of this underscreening for soft-matter and colloidal systems by investigating the stability of nanoparticle dispersions, the self-assembly of ionic surfactants, and the thickness of soap films. In each case, we find clear evidence of re-entrant properties due to underscreening at high salt concentrations. Our results show that underscreening in concentrated electrolytes is a general phenomenon and is not dependent on confinement by macroscopic surfaces. The stability of systems at very high salinity due to underscreening may be beneficially applied to processes that currently use low-salinity water.

18.
Nanomicro Lett ; 13(1): 177, 2021 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-34403020

RESUMO

Passivation, as a classical surface treatment technique, has been widely accepted in start-of-the-art perovskite solar cells (PSCs) that can effectively modulate the electronic and chemical property of defective perovskite surface. The discovery of inorganic passivation compounds, such as oxysalts, has largely advanced the efficiency and lifetime of PSCs on account of its favorable electrical property and remarkable inherent stability, but a lack of deep understanding of how its local configuration affects the passivation effectiveness is a huge impediment for future interfacial molecular engineering. Here, we demonstrate the central-atom-dependent-passivation of oxysalt on perovskite surface, in which the central atoms of oxyacid anions dominate the interfacial oxygen-bridge strength. We revealed that the balance of local interactions between the central atoms of oxyacid anions (e.g., N, C, S, P, Si) and the metal cations on perovskite surface (e.g., Pb) generally determines the bond formation at oxysalt/perovskite interface, which can be understood by the bond order conservation principle. Silicate with less electronegative Si central atoms provides strong O-Pb motif and improved passivation effect, delivering a champion efficiency of 17.26% for CsPbI2Br solar cells. Our strategy is also universally effective in improving the device performance of several commonly used perovskite compositions.

19.
Chem Commun (Camb) ; 56(96): 15201-15204, 2020 Dec 08.
Artigo em Inglês | MEDLINE | ID: mdl-33227114

RESUMO

Revealing how to rationally select a suitable dopant or the host counterpart is greatly important for optimizing the catalytic activity of transition metal oxides (TMOs). We systematically report the adsorption trends of atomic O and H, two selected representative adsorbates, on numerous doped rutile-type TMO surfaces under two different doping modes, aiming to demonstrate adsorption energy (AE) variations of different adsorbates across doped TMO surfaces. A "host-guest interaction" induced adsorption tuning rule for the ternary doping systems is identified, which rationally directs the proposal of cost-effective Ir-doped CrO2 or MnO2 catalysts for the electrocatalytic oxygen evolution reaction compared with the common IrO2.

20.
Soft Matter ; 16(17): 4087-4104, 2020 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-32292998

RESUMO

The ionic effects on synthetic polymers have attracted extensive attention due to the crucial role of ions in the determination of the properties of synthetic polymers. This review places the focus on specific ion effects, multivalent ion effects, and ionic hydrophilicity/hydrophobicity effects in synthetic polymer systems from solutions to brushes and gels. The specific ion effects on neutral polymers are determined by both the direct and indirect specific ion-polymer interactions, whereas the ion specificities of charged polymers are mainly dominated by the specific ion-pairing interactions. The ionic cross-linking effect exerted by the multivalent ions is widely used to tune the properties of polyelectrolytes, while the reentrant behavior of polyelectrolytes in the presence of multivalent ions still remains poorly understood. The ionic hydrophilicity/hydrophobicity effects not only can be applied to make strong polyelectrolytes thermosensitive, but also can be used to prepare polymeric nano-objects and to control the wettability of polyelectrolyte brush-modified surfaces. The not well-studied ionic hydrogen bond effects are also discussed in the last section of this review.

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