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1.
Sensors (Basel) ; 24(9)2024 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-38732931

RESUMO

The attributes of diversity and concealment pose formidable challenges in the accurate detection and efficacious management of distresses within subgrade structures. The onset of subgrade distresses may precipitate structural degradation, thereby amplifying the frequency of traffic incidents and instigating economic ramifications. Accurate and timely detection of subgrade distresses is essential for maintaining and repairing road sections with existing distresses. This helps to prolong the service life of road infrastructure and reduce financial burden. In recent years, the advent of numerous novel technologies and methodologies has propelled significant advancements in subgrade distress detection. Therefore, this review delineates a concentrated examination of subgrade distress detection, methodically consolidating and presenting various techniques while dissecting their respective merits and constraints. By furnishing comprehensive guidance on subgrade distress detection, this review facilitates the expedient identification and targeted treatment of subgrade distresses, thereby fortifying safety and enhancing durability. The pivotal role of this review in bolstering the construction and operational facets of transportation infrastructure is underscored.

2.
Adv Mater ; : e2400648, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38488330

RESUMO

The increasingly severe plastic pollution has urged an inevitable trend to develop biodegradable plastic products that can take over synthetic plastics. As one of the most abundant natural polymers, polysaccharides are an ideal candidate to substitute synthetic plastics. The rigidity of polysaccharide chains principally allows for high strength and stiffness of their materials, however, challenges the facile orientation in material processing. Here, a general hydrogen bond-mediated plasticization strategy to regulate isotropic sodium alginate (SA) chains to a highly ordered state is developed, and alginate plastics with high performances are fabricated. It is revealed that hydroxyl groups in glycerol modulate the viscoelasticity of SA solids by forming strong hydrogen bonds with SA chains, achieving a large stretchability at a high solid content. Highly orientated alginate films exhibit a superior tensile strength of 575 MPa and toughness of 60.7 MJ m-3, outperforming most regenerated biomass films. The high solid content and large stretchability mediated by strong hydrogen bonding ensure plastic molding of solid-like SA with high fidelity. This hydrogen bond-mediated plasticity provides a facile but effective method to justify the high performances of polysaccharide-based plastics.

3.
Environ Res ; 248: 118409, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38311203

RESUMO

A huge production of waste activated sludge (WAS) has been a burden for wastewater treatment plants (WWTPs) with high disposal cost and little benefit back to wastewater purification. The short-chain fatty acids (SCFAs) produced by a short-term acidogenic fermentation of WAS before methane production have been proven to be a high-quality carbon source available for microbial denitrification process. The dual purpose of full recovery of fermentation liquid products and facilitating disposal of residual solid waste necessitate an efficient solid-liquid separation process of short-term fermentation liquid. The transformation and loss of various soluble carbon sources between solid and liquid are very important issues for carbon recovery efficiency when combining short-term fermentation and sludge dewatering in WWTPs. Here we testified the three conventional preconditioning coagulants, Polyferric Sulfate (PFS), Poly Aluminum Chloride (PAC) and Polyacrylamide (PAM), to improve the efficiency of subsequent solid-liquid separation. The results show that conversion yield of SCFAs in the liquid phase of sludge after short-term fermentation was 195 mg COD/g VSS, when using the coagulants PFS, PAC, and PAM for recovery, the recovery ratio was 79.5%, 82.0%, and 85.9%, respectively, while the dewaterability could be improved after preconditioning short-term fermentation sludge. The complexation of Al3+/Fe3+ in metal coagulants with carboxyl groups of SCFA demonstrated by Density Functional Theory calculation led to small part of soluble carbons co-migration to the solid phase, mainly a loss of high molecular weight organic compounds (carbohydrate, proteins, humic acids), while the application of PAM had little impact on carbon recovery. Economic calculations further showed PAM preconditioning short-term fermentation liquid of WAS could achieve higher recovery benefits.


Assuntos
Esgotos , Purificação da Água , Fermentação , Carbono , Ácidos Graxos Voláteis
4.
Eur J Med Chem ; 264: 115979, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38048696

RESUMO

Although no longer a public health emergency of international concern, COVID-19 remains a persistent and critical health concern. The development of effective antiviral drugs could serve as the ultimate piece of the puzzle to curbing this global crisis. 3-chymotrypsin-like protease (3CLpro), with its substrate specificity mirroring that of the main picornavirus 3C protease and conserved across various coronaviruses, emerges as an ideal candidate for broad-spectrum antiviral drug development. Moreover, it holds the potential as a reliable contingency option to combat emerging SARS-CoV-2 variants. In this light, the approved drugs, promising candidates, and de-novo small molecule therapeutics targeting 3CLpro since the COVID-19 outbreak in 2020 are discussed. Emphasizing the significance of diverse structural characteristics in inhibitors, be they peptidomimetic or nonpeptidic, with a shared mission to minimize the risk of cross-resistance. Moreover, the authors propose an innovative optimization strategy for 3CLpro reversible covalent PROTACs, optimizing pharmacodynamics and pharmacokinetics to better prepare for potential future viral outbreaks.


Assuntos
COVID-19 , Humanos , Quimases , SARS-CoV-2 , Inibidores de Proteases/farmacologia , Inibidores de Proteases/química , Surtos de Doenças , Antivirais/farmacologia , Antivirais/química
5.
J Am Chem Soc ; 145(50): 27639-27649, 2023 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-38054305

RESUMO

While chiral molecular rotors have unique frames and cavities to possibly generate switchable chiroptical functions, it still remains a formidable challenge to precisely restrict their rotations to activate certain functions such as fluorescence as well as circularly polarized luminescence (CPL), which are strongly related to the local molecular rotations. Herein, we design a pair of enantiopure helical cage rotors, which emit light neither at the molecular state nor in the crystal or aggregation states, although they contain luminophore groups. However, upon mounting with fluoroaromatic borane (TFPB) as a molecular brake, the phenyl rotation of the helical cage can be effectively hindered and fluorescence and CPL activities of the molecular cage are switched on. Crystal structure analysis reveals that the rotation is restricted through synergistic B-O-H-N bonding and a fluoroaromatic-aromatic (ArF-Ar) dipole interaction. Moreover, the helical cages are switched on stepwise with color-variable fluorescence and CPL by the inner brake in the molecular state and the outer brake in the supramolecular assemblies, respectively. This work not only provides the design idea of chiroptical molecular rotors but also unveils how fluorescence and CPL could be generated in cage rotor systems.

6.
Redox Biol ; 67: 102871, 2023 11.
Artigo em Inglês | MEDLINE | ID: mdl-37699320

RESUMO

Ferroptosis is a newly discovered form of iron-dependent oxidative cell death and drives the loss of neurons in spinal cord injury (SCI). Mitochondrial damage is a critical contributor to neuronal death, while mitochondrial quality control (MQC) is an essential process for maintaining mitochondrial homeostasis to promote neuronal survival. However, the role of MQC in neuronal ferroptosis has not been clearly elucidated. Here, we further demonstrate that neurons primarily suffer from ferroptosis in SCI at the single-cell RNA sequencing level. Mechanistically, disordered MQC aggravates ferroptosis through excessive mitochondrial fission and mitophagy. Furthermore, mesenchymal stem cells (MSCs)-mediated mitochondrial transfer restores neuronal mitochondria pool and inhibits ferroptosis through mitochondrial fusion by intercellular tunneling nanotubes. Collectively, these results not only suggest that neuronal ferroptosis is regulated in an MQC-dependent manner, but also fulfill the molecular mechanism by which MSCs attenuate neuronal ferroptosis at the subcellular organelle level. More importantly, it provides a promising clinical translation strategy based on stem cell-mediated mitochondrial therapy for mitochondria-related central nervous system disorders.


Assuntos
Ferroptose , Células-Tronco Mesenquimais , Traumatismos da Medula Espinal , Humanos , Traumatismos da Medula Espinal/genética , Traumatismos da Medula Espinal/terapia , Traumatismos da Medula Espinal/metabolismo , Neurônios/metabolismo , Mitocôndrias/metabolismo , Células-Tronco Mesenquimais/metabolismo
7.
Genes Dis ; 10(4): 1596-1612, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37397525

RESUMO

Non-alcoholic steatohepatitis (NASH), a progressive form of non-alcoholic fatty liver disease (NAFLD), is characterised by chronic liver inflammation, which can further progress into complications such as liver cirrhosis and NASH-associated hepatocellular carcinoma (HCC) and therefore has become a growing health problem worldwide. The type I interferon (IFN) signaling pathway plays a pivotal role in chronic inflammation; however, the molecular mechanisms underlying NAFLD/NASH from the perspective of innate immune response has not yet been fully explored. In this study, we elucidated the mechanisms of how innate immune response modulates NAFLD/NASH pathogenesis, and demonstrated that hepatocyte nuclear factor-1alpha (HNF1A) was suppressed and the type I IFN production pathway was activated in liver tissues of patients with NAFLD/NASH. Further experiments suggested that HNF1A negatively regulates the TBK1-IRF3 signaling pathway by promoting autophagic degradation of phosphorylated-TBK1, which constrains IFN production, thereby inhibiting the activation of type I IFN signaling. Mechanistically, HNF1A interacts with the phagophore membrane protein LC3 through its LIR-docking sites, and mutations of LIRs (LIR2, LIR3, LIR4, and LIRs) block the HNF1A-LC3 interaction. In addition, HNF1A was identified not only as a novel autophagic cargo receptor but also to specifically induce K33-linked ubiquitin chains on TBK1 at Lys670, thereby resulting in autophagic degradation of TBK1. Collectively, our study illustrates the crucial function of the HNF1A-TBK1 signaling axis in NAFLD/NASH pathogenesis via cross-talk between autophagy and innate immunity.

8.
Front Psychiatry ; 14: 1156149, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37304431

RESUMO

Background: Polydrug abuse is common among opioid users. Individuals who use both heroin and methamphetamine (MA) have been shown to experience a wide range of cognitive deficits. Previous research shows that repetitive transcranial magnetic stimulation (rTMS) can change cerebral cortical excitability and regulate neurotransmitter concentration, which could improve cognitive function in drug addiction. However, the stimulation time, location, and possible mechanisms of rTMS are uncertain. Methods: 56 patients with polydrug use disorder were randomized to receive 20 sessions of 10 Hz rTMS (n = 19), iTBS (n = 19), or sham iTBS (n = 18) to the left DLPFC. All patients used MA and heroin concurrently. Cognitive function was assessed and several related proteins including EPI, GABA-Aα5, IL-10, etc. were quantified by ELISA before and after the treatment. Results: Baseline RBANS scores were lower than normal for age (77.25; IQR 71.5-85.5). After 20 treatment sessions, in the iTBS group, the RBANS score increased by 11.95 (95% CI 0.02-13.90, p = 0.05). In particular, there were improvements in memory and attention as well as social cognition. Following treatment, serum EPI and GABA-Aα5 were reduced and IL-10 was elevated. The improvement of immediate memory was negatively correlated with GABA-Aα5 (r = -0.646, p = 0.017), and attention was positively correlated with IL-10 (r = 0.610, p = 0.027). In the 10 Hz rTMS group, the improvement of the RBANS total score (80.21 ± 14.08 before vs.84.32 ± 13.80 after) and immediate memory (74.53 ± 16.65 before vs.77.53 ± 17.78 after) was statistically significant compared with the baseline (p < 0.05). However, compared with the iTBS group, the improvement was small and the difference was statistically significant. There was no statistically significant change in the sham group (78.00 ± 12.91 before vs.79.89 ± 10.92 after; p > 0.05). Conclusion: Intermittent theta burst stimulation to the left DLPFC may improve cognitive function in polydrug use disorder patients. Its efficacy appears to be better than that of 10 Hz rTMS. The improvement of cognitive function may be related to GABA-Aα5 and IL-10. Our findings preliminarily demonstrate the clinical value of iTBS to the DLPFC to augment neurocognitive recovery in polydrug use disorders.

9.
Appl Microbiol Biotechnol ; 107(11): 3523-3533, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-37145161

RESUMO

L-Alanyl-L-Glutamine (Ala-Gln) is a common parenteral nutritional supplement. In our previous study, the recombinant whole-cell catalyst Escherichia coli BL21(DE3) overexpressing α-amino acid ester acyltransferase (BPA) to produce Ala-Gln has high activity and has been applied to large-scale production experiments. However, the degradation of Ala-Gln is detected under prolonged incubation, and endogenous broad-spectrum dipeptidase may be the primary cause. In this study, a CRISPR-Cas9 method was used to target pepA, pepB, pepD, pepN, dpp, and dtp to knock out one or more target genes. The deletion combination was optimized, and a triple knockout strain BL21(DE3)-ΔpepADN was constructed. The degradation performance of the knockout chassis was measured, and the results showed that the degradation rate of Ala-Gln was alleviated by 48% compared with the control. On this basis, BpADNPA (BPA-ΔpepADN) was built, and the production of Ala-Gln was 129% of the BPA's accumulation, proving that the ΔpepADN knockout conducive to the accumulation of dipeptide. This study will push forward the industrialization process of Ala-Gln production by whole-cell catalyst Escherichia coli expressing α-amino acid ester acyltransferase. KEY POINTS: • Endogenous dipeptidase knockout alleviates the degradation of Ala-Gln by the chassis • The balanced gene knockout combination is pepA, pepD, and pepN • The accumulation of Ala-Gln with BpADNPA was 129% of the control.


Assuntos
Aminoácidos , Dipeptidases , Aminoácidos/metabolismo , Escherichia coli/genética , Escherichia coli/metabolismo , Dipeptidases/metabolismo , Aciltransferases/genética , Aciltransferases/metabolismo , Técnicas de Inativação de Genes , Dipeptídeos/metabolismo , Glutamina/metabolismo
10.
Chemosphere ; 335: 139048, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37245593

RESUMO

Calcium alginate (CA) hydrogel spheres were widely used as adsorbents to remove organics, but their adsorption capacities and reusability to some antibiotics are unsatisfactory. In this study, calcium alginate/chitosan (CA/CTS) hydrogel spheres were prepared as precursors. Acid-washed CA/CTS (CA/CTS-M) hydrogel spheres (310.6 mg/g) behaved much better adsorption capacity of norfloxacin (NOR) than CA (69.5 mg/g) and CA/CTS (87.7 mg/g) hydrogel spheres. Astonishingly, after being reused for 15 cycles, CA/CTS-M has no loss of NOR adsorption capacity. In the original idea, acid wash was expected to remove the chitosan in CA/CTS hydrogel spheres for obtaining a larger specific surface area. Both scanning electron microscopy and Brunauer-Emmett-Teller test showed that acid wash can remove CTS from CA/CTS hydrogel spheres to increase the specific surface area. However, part of the chitosan remained in CA/CTS-M, having a role to enhance the structural stability of the material, because the acid-washed CA (about 2 mm) has a significantly smaller diameter than CA/CTS-M (about 3 mm). According to the influence of pH and density functional theory calculations, electrostatic attraction is the key driving force of NOR adsorption. Importantly, acid wash led to more negative-charged surface characterized by Zeta potential, which is the main reason of the significantly enhanced adsorption capacity of CA/CTS-M in removal of NOR. In short, CA/CTS-M hydrogel spheres are environment friendly and highly stable adsorbents with high adsorption capacity in the removal of NOR.


Assuntos
Quitosana , Poluentes Químicos da Água , Norfloxacino , Hidrogéis , Adsorção , Alginatos , Concentração de Íons de Hidrogênio , Cinética
11.
Hepatol Int ; 17(4): 850-859, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37067675

RESUMO

BACKGROUND AND AIMS: Liver transplantation (LT) is the primary curative option for cirrhotic patients with early-stage hepatocellular carcinoma (HCC). However, tumor recurrence occurs in 15-20% of cases with unfavorable prognosis. We have developed a library of T cell receptors (TCRs) specific for different hepatitis B virus (HBV) antigens, restricted by different molecules of human leucocyte antigen (HLA)-class I, to redirect T cells against HBV antigens (Banu in Sci Rep 4:4166, 2014). We further demonstrated that these transiently functional T cells specific for HBV obtained through messenger RNA (mRNA) electroporation can eliminate HCC cells expressing HBV antigens in vitro and in vivo (Kah in J Clin Invest 127:3177-3188, 2017). A phase I clinical trial for patients with HCC recurrence post-liver transplant was conducted to assess the safety, tolerability, and anti-tumor efficacy of transiently functional HBV-TCR T cells. Here, we report the clinical findings with regard to the safety and anti-tumor efficacy of mRNA electroporated HBV-specific TCR-T cells. (ClinicalTrials.gov identifier: NCT02719782). PATIENTS AND METHODS: A total of six patients with HBV-positive recurrent HCC post-liver transplant and HLA-matched to TCR targeting hepatitis B surface antigen (HBsAg) or hepatitis B core antigen (HBcAg) (HLA-A*02:01/HBsAg, HLA-A*11:01/HBcAg, HLA-B*58:01/HBsAg or HLA-C*08:01/HBsAg) were enrolled in this study. The primary objective was to assess the safety of short-lived mRNA electroporated HBV-TCR T cells based on the incidence and severity of the adverse event (AE) graded per National Cancer Institute Common Terminology Criteria for Adverse Events (NCI CTCAE), Version 4.0. The secondary objective was to determine the effectiveness of HBV-TCR T cells as per RECIST 1.1 criteria. Patients were followed up for survival for 2 years post-end of treatment. RESULTS: The median age of the six patients was 35.5 years (range: 28-47). The median number of HBV-TCR T cell infusions administered was 6.5 (range: 4-12). The treatment-related AE included grade 1 pyrexia. This study reported no cytokine release syndrome nor neurotoxicity. One patient remained alive and five were deceased at the time of the data cutoff (30 April 2020). CONCLUSION: This study has demonstrated that multiple infusions of mRNA electroporated HBV-specific TCR T cells were well-tolerated in patients with HBV-positive recurrent HCC post-liver transplant.


Assuntos
Carcinoma Hepatocelular , Hepatite B , Neoplasias Hepáticas , Transplante de Fígado , Humanos , Adulto , Pessoa de Meia-Idade , Vírus da Hepatite B/genética , Antígenos de Superfície da Hepatite B , Neoplasias Hepáticas/patologia , Antígenos do Núcleo do Vírus da Hepatite B/uso terapêutico , RNA Mensageiro , Recidiva Local de Neoplasia/terapia , Recidiva Local de Neoplasia/complicações , Receptores de Antígenos de Linfócitos T/genética , Hepatite B/complicações
12.
J Agric Food Chem ; 71(16): 6398-6405, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37027821

RESUMO

l-Alanyl-l-glutamine (Ala-Gln) is a widely used value-added dipeptide whose production relies heavily upon an efficient biocatalyst. The currently available yeast biocatalysts that express α-amino acid ester acyltransferase (SsAet) possess relatively low activity, which may be attributed to glycosylation. Here, to promote SsAet activity in yeast, we identified the N-glycosylation site as the Asn residue at position 442 and subsequently eliminated the negative effect of N-glycosylation on SsAet by removing artificial and native signal peptides to obtain K3A1, a novel yeast biocatalyst with significantly improved activity. Additionally, the optimal reaction conditions of strain K3A1 were determined (25 °C, pH 8.5, AlaOMe/Gln = 1:2), resulting in a maximum molar yield and productivity of approximately 80% and 1.74 g·(L·min)-1, respectively. Therefore, we developed a promising system to cleanly produce Ala-Gln in a safe, efficient, and sustainable manner, which may contribute to the future industrial production of Ala-Gln.


Assuntos
Aciltransferases , Glutamina , Aminoácidos , Dipeptídeos/química , Glutamina/metabolismo , Glicosilação , Saccharomyces cerevisiae/genética , Saccharomyces cerevisiae/metabolismo , Biocatálise
13.
J Control Release ; 356: 402-415, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-36858264

RESUMO

Aging is one of the critical factors to impair liver regeneration leading to a high incidence of severe complications after hepatic surgery in the elderly population without any effective treatment for clinical administration. As cell-free nanotherapeutics, mesenchymal stem cell-derived extracellular vesicles (MSC-EVs) have been demonstrated the therapeutic potentials on liver diseases. However, the effects of MSC-EVs on the proliferation of aged hepatocytes are largely unclear. In this study, we found MSCs could reduce the expression of senescence-associated markers in the liver and stimulate its regeneration in aged mice after receiving a two-thirds partial hepatectomy (PHx) through their secreted MSC-EVs. Using RNA-Seq and AAV9 vector, we mechanistically found that these effects of UC-MSC-EVs partially attributed to inducing Atg4B-related mitophagy. This effect repairs the mitochondrial status and functions of aged hepatocytes to promote their proliferation. And protein mass spectrum analysis uncovered that DEAD-Box Helicase 5 (DDX5) enriches in UC-MSC-EVs, which interacts with E2F1 to facilitate its nuclear translocation for activating the expression of Atg4B. Collectively, our data show that MSC-EVs act nanotherapeutic potentials in anti-senescence and promoting regeneration of aged liver by transferring DDX5 to regulate E2F1-Atg4B signaling pathway that induce mitophagy, which highlights the clinical application valuation of MSC-EVs for preventing severe complications in aged population receiving liver surgery.


Assuntos
Vesículas Extracelulares , Hepatopatias , Idoso , Humanos , Camundongos , Animais , Regeneração Hepática , Hepatócitos/metabolismo , Vesículas Extracelulares/metabolismo , RNA Helicases DEAD-box/metabolismo
14.
Environ Pollut ; 316(Pt 1): 120572, 2023 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-36335784

RESUMO

Various hydrogen bonds, especially charge-assisted hydrogen bond (CAHB), is considered as one of vital mechanisms affecting the environmental behavior and risk of pharmaceutical contaminants (PCs). Herein the sorption/desorption of three PCs including clofibric acid (CA), acetaminophen (ACT), and sulfamerazine (SMZ) on three Oxygen-rich (O-rich) nanoparticles (nano-silica: Nano-SiO2, nano-alumina: Nano-Al2O3, and oxidized carbon nanotubes: O-CNTs) were investigated to explore the effect of various hydrogen bonds with different strengths on environmental behaviors of PCs. The results indicated that although solvent-assisted CAHB, solvent-uninvolved CAHB, and ordinary hydrogen bond (OHB) all played a crucial role in sorption of PCs on three O-rich nanomaterials, they showed significantly different effects on the desorption behaviors of PCs from three sorbents. Compared with OHB (hysteresis index ≤0.0766), the stronger CAHB (hysteresis index ≥0.1981) between PCs and O-rich nanoparticles having comparable pKa with PCs, caused obvious desorption hysteresis of PCs, resulting in their better immobilization on O-rich nanomaterials. The FTIR characterization found that both solvent-assisted and solvent-uninvolved CAHB formation resulted in a new characteristic peak appeared in the high frequency (3660 cm-1 for Nano-SiO2, 3730 cm-1 for Nano-Al2O3, and 3780 cm-1 for O-CNTs). Also, density functional theory (DFT) calculation verified that the smaller |ΔpKa| between PCs and O-rich sorbents, the shorter bond length, and the larger bond angle resulted in the stronger hydrogen bond formed, thereby leading to the greater immobilization of PCs. These results provide in-depth understanding of the environmental behavior and risk of PCs, and light new idea for designed materials to control PCs pollution in the environment.


Assuntos
Nanotubos de Carbono , Ligação de Hidrogênio , Adsorção , Nanotubos de Carbono/química , Oxigênio , Dióxido de Silício , Solventes , Preparações Farmacêuticas
15.
Sci Total Environ ; 861: 160623, 2023 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-36460113

RESUMO

The effect of various hydrogen bonds with different strength on the environmental behaviors of PPCPs remains unclear. In this study, three pharmaceutical pollutants including clofibric acid (CA), sulfamerazine (SMZ), and acetaminophen (ACT) with different functional groups and pKa, were selected as representative of PPCPs to investigate the pivotal role of hydrogen bonds in adsorption/desorption and co-adsorption behaviors of PPCPs on two corn straw-derived biochars prepared at 300 °C (BCs-300) and 600 °C (BCs-600), respectively. The results indicated that charge-assisted hydrogen bond (CAHB) and ordinary hydrogen bond (OHB) with different intensities were the pivotal mechanisms responsible for the adsorption of three PPCPs on biochars, which was further confirmed by FTIR, but their immobilization effects of PPCPs on biochars were completely different. Compared with OHB formed between CA and BCs-600, the stronger CAHB (formed between CA and BCs-300, and SMZ/ACT and BCs-300/BCs-600) with covalent bond characteristics that derived from the smaller |ΔpKa| (<5.0), resulted in the greater adsorption capacity (Qs) and affinity (Kf) of the three PPCPs on BCs-300 (Qs ≥ 195 µmol·g-1, Kf ≥ 1.9956) than that on BCs-600 (Qs ≤ 92 µmol·g-1, Kf ≤ 0.5192), thereby making the better immobilization effect of PPCPs by biochar. In addition, in the coexisting systems, either SMZ coexisting with CA/ACT on BCs-300, or ACT coexisting with CA/SMZ on BCs-600, both implied that when the |ΔpKa| between the target PPCPs and biochar is smaller than that between the coexisting compound and biochar, the target PPCPs can preferentially occupy the shared hydrogen bond sites on the biochar surface, and hard to be replaced by the coexisting compound. This work not only expand the application of designed biochar as engineering adsorbents to control and removal of the specific PPCPs in the environment, but also facilitate accurate assessment of the environmental risk of co-existing PPCPs.


Assuntos
Carvão Vegetal , Zea mays , Ligação de Hidrogênio , Adsorção , Carvão Vegetal/química
16.
Sci Rep ; 12(1): 18578, 2022 11 03.
Artigo em Inglês | MEDLINE | ID: mdl-36329161

RESUMO

Protecting and restoring the degraded arid lakes are globally urgent issues. We document a potential recovery of the dried salt-lake, Lop Nur called "the Sea of Death" which is located at the terminus of the largest inland basin in China, the Tarim River Basin. The changes and relationship of surface water with climate parameters and groundwater in the basin over the last 30 years are analyzed, by using satellite remote sensing and land data assimilation products. We find that with increased surface water in the basin, the groundwater level in Lop Nur began to show an obvious positive response in 2015; and the rate of decline of the groundwater level is slowing down. We argue that after a balance is achieved between regional groundwater recharge and evapotranspiration, the Lop Nur ecosystem will gradually recover. This study shows an encouraging case for the protection and restoration of degraded lakes in dryland regions around the world.


Assuntos
Água Subterrânea , Lagos , Ecossistema , Água , Rios , Abastecimento de Água , China , Monitoramento Ambiental
17.
Nat Nanotechnol ; 17(12): 1294-1302, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36329269

RESUMO

Fabricating microscale helical structures from small molecules remains challenging due to the disfavoured torsion energy of twisted architectures and elusory chirality control at different hierarchical levels of assemblies. Here we report a combined solution-interface-directed assembly strategy for the formation of hierarchically self-assembled helical microtoroids with micrometre-scale lengths. A drop-evaporation assembly protocol on a solid substrate from pre-assembled intermediate colloids of enantiomeric binaphthalene bisurea compounds leads to microtoroids with preferred helicity, which depends on the molecular chirality of the starting enantiomers. Collective variable-temperature spectroscopic analyses, electron microscopy characterizations and theoretical simulations reveal a mechanism that simultaneously induces aggregation and cyclization to impart a favourable handedness to the final microtoroidal structures. We then use monodispersed luminescent helical toroids as chiral light-harvesting antenna and show excellent Förster resonance energy transfer ability to a co-hosted chiral acceptor dye, leading to unique circularly polarized luminescence. Our results shed light on the potential of the combined solution-interface-directed self-assembly approach in directing hierarchical chirality control and may advance the prospect of chiral superstructures at a higher length scale.


Assuntos
Luminescência , Estereoisomerismo
18.
Materials (Basel) ; 15(19)2022 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-36234153

RESUMO

Conventional asphalt pavement has a deep surface color and large thermal inertia, which leads to the continuous absorption of solar thermal radiation and the sharp rise of surface temperature. This can easily lead to the permanent deformation of pavement, as well as aggravate the urban heat island (UHI) effect. Cool pavement with a reflective coating plays an important role in reducing pavement temperature and alleviating the UHI effect. It is of great significance to study the influence of temperature on the mechanical response of different types of pavement under vehicle loading. Therefore, this study examined the heat exchange theory between pavement and the external environment and utilized the representative climate data of a 24 h period in the summer. Two kinds of three-dimensional finite element models were established for the analysis of temperature distribution and the mechanical responses of conventional pavement and cool pavement. The results show that in this environmental condition, conventional pavement temperatures can exceed 50 °C under high temperatures in summer, which allows for the permanent deformation of pavement and further affects the service life of asphalt pavement. The temperature difference in a conventional pavement surface between 6 h (24.7 °C) and 22 h (30.2 °C) is much less than that between 22 h (30.2 °C) and 13 h (50.1 °C) in the summer. However, the difference in the vertical displacements of the pavement surface between 6 h and 22 h is much larger than that between 22 h and 13 h. One reason is that the difference in temperature distribution between the morning and night leads to changes in pavement structure stiffness, resulting in significant differences in vertical displacement. Cool pavement has a significant cooling effect, which can reduce the surface temperature of a road by more than 15 °C and reduce the vertical displacement of the pavement by approximately 11.3%, which improves the rutting resistance of the pavement. However, the use of cool pavement will not change the horizontal strain at the bottom of the asphalt base and will not improve the fatigue resistance of asphalt pavement. This research will lay the foundation for further clarifying the difference in the mechanical properties between the two types of pavements in the management and maintenance stage.

19.
Artigo em Inglês | MEDLINE | ID: mdl-36231423

RESUMO

Herein, the adsorption/desorption behaviors of benzoic acid (BA) and phthalic acid (PA) on three functionalized carbon nanotubes (CNTs) at various pH were investigated, and the charge-assisted H-bond (CAHB) was verified by DFT and FTIR analyses to play a key role. The results indicated that the adsorption order of BA and PA on CNTs was different from Kow of that at pH 2.0, 4.0, and 7.0 caused by the CAHB interaction. The strength of homonuclear CAHB (≥78.96 kJ·mol-1) formed by BA/PA on oxidized CNTs is stronger than that of heteronuclear CAHB formed between BA/PA and amino-functionalized CNTs (≤51.66 kJ·mol-1). Compared with the heteronuclear CAHB (Hysteresis index, HI ≥ 1.47), the stronger homonuclear CAHB leads to clearly desorption hysteresis (HI ≥ 3.51). Additionally, the contribution of homonuclear CAHB (≥52.70%) was also greater than that of heteronuclear CAHB (≤45.79%) at pH 7.0. These conclusions were further confirmed by FTIR and DFT calculation, and the crucial evidence of CAHB formation in FTIR was found. The highlight of this work is the identification of the importance and difference of pH-dependent homonuclear/heteronuclear CAHB on the adsorption and desorption behaviors of ionizable organic compounds on carbonaceous materials, which can provide a deeper understanding for the removal of ionizable organic compounds by designed carbonaceous materials.


Assuntos
Nanotubos de Carbono , Adsorção , Ácido Benzoico , Concentração de Íons de Hidrogênio , Nanotubos de Carbono/química , Compostos Orgânicos/química
20.
J Assist Reprod Genet ; 39(8): 1779-1787, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35870097

RESUMO

PURPOSE: Testicular sperm aspiration (TESA) is widely used to retrieve sperm from testis. Diagnostic testicular biopsy should not be routinely performed for azoospermia. Therefore, a good predictive model is needed before TESA. METHODS: A total of 1972 azoospermia patients constituted the modelling set, and 260 azoospermia patients from two other centres constituted the validation set. An integrated predictive model was built using logistic regression. Receiver operating characteristic (ROC), calibration and decision curve analyses were performed to evaluate the performance of follicle-stimulating hormone (FSH), semen volume, testicular volume and the integrated model. RESULTS: The FSH level was the best univariate predictor for successful sperm retrieval (SSR) and was better than semen volume and testicular volume alone (p<0.001, threshold 6.17 IU/L, modelling set area under receiver operating characteristic curve (AUC) 0.80, accuracy 0.79; validation set AUC 0.87, accuracy 0.78). The integrated predictive model had excellent accuracy for predicting SSR (modelling set: AUC 0.93, accuracy 0.89; validation set: AUC 0.96, accuracy: 0.89). Calibration curve analysis indicated that the integrated model calibration was good and better than that of FSH, semen volume and testicular volume alone. Decision curve analysis indicated with a threshold probability between 0.05 and 0.98, the integrated model added more benefit than treating either all or no patients. CONCLUSIONS: The integrated model has excellent discrimination and good calibration. It can help azoospermic men make better decisions before TESA. It should be noted that TESA is not the first-line treatment for non-obstructive azoospermia because of a low sperm retrieval rate.


Assuntos
Azoospermia , Recuperação Espermática , Azoospermia/patologia , Estudos de Coortes , Hormônio Foliculoestimulante , Humanos , Masculino , Estudos Retrospectivos , Sêmen , Espermatozoides/patologia , Testículo/patologia
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