RÉSUMÉ
Low-molecular weight proteins (LWPs) are important sources of biological information in biomarkers, signaling molecules, and pathology. However, the separation and analysis of LWPs in complex biological samples are challenging, mainly due to their low abundance and the complex sample pretreatment procedure. Herein, trypsin modified by poly(acrylic acid) (PAA) was encapsulated by a zeolitic imidazolate framework (ZIF-L). Mesopores were formed on the ZIF-L with the introduction of PAA. An alternative strategy for separation and pretreatment of LWPs was developed based on the prepared ZIF-L-encapsulated trypsin with adjustable pore size. The mesoporous structure of the prepared materials selectively excluded high-molecular weight proteins from the reaction system, allowing LWPs to enter the pores and react with the internal trypsin, resulting in an improved separation efficiency. The hydrophobicity of the ZIF-L simplified the digestion process by inducing significant structural changes in substrate proteins. In addition, the enzymatic activity was significantly enhanced by the developed encapsulation method that maintained the enzyme conformation, allowed low mass transfer resistance, and possessed a high enzyme-to-substrate ratio. As a result, the ZIF-L-encapsulated trypsin can achieve highly selective separation, valid denaturation, and efficient digestion of LWPs in a short time by simply mixing with substrate proteins, greatly simplifying the separation and pretreatment process of the traditional hydrolysis method. The prepared materials and the developed strategy demonstrated an excellent size-selective assay performance in model protein mixtures, showing great potential in the application of proteomics analysis.
Sujet(s)
Imidazoles , Trypsine , Zéolites , Trypsine/composition chimique , Trypsine/métabolisme , Zéolites/composition chimique , Imidazoles/composition chimique , Masse moléculaire , Résines acryliques/composition chimique , Porosité , Protéines/composition chimiqueRÉSUMÉ
In situ monitoring of intracellular microRNAs (miRNAs) often encounters the challenges of surrounding complexity, coexistence of precursor miRNAs (pre-miRNAs) and the degradation of biological enzyme in living cells. Here, we designed a novel probe encapsulated DNA tetrahedral molecular sieve (DTMS) to realize the size-selective detection of intracellular miRNA 21 that can avoid the interference of pre-miRNAs. In such strategy, quencher (BHQ-1) labeled probe DNA (S6-BHQ 1) was introduced into the inner cavity of fluorophore (FAM) labeled DNA tetrahedral scaffolds (DTS) to prepare DTMS, making the FAM and BHQ-1 closely proximate, and resulting the sensor in a "signal-off" state. In the presence of miRNA 21, strand displacement reaction happened to form more stable DNA double-stranded structure, accompanied by the release of S6-BHQ 1 from the inner cavity of DTMS, making the sensor in a "signal-on" state. The DTMS based sensing platform can then realized the size-selective detection of miRNA 21 with a detection limit of 3.6 pM. Relying on the mechanical rigidity of DTS and the encapsulation of DNA probe using DTMS, such proposed method achieved preferable reproducibility and storage stability. Moreover, this sensing system exhibited good performance for monitoring the change of intracellular miRNA 21 level during the treatment with miRNA-related drugs, demonstrating great potential for biological studies and accurate disease diagnosis.
Sujet(s)
ADN , Colorants fluorescents , microARN , microARN/analyse , Humains , ADN/composition chimique , Colorants fluorescents/composition chimique , Spectrométrie de fluorescence/méthodes , Limite de détection , Sondes d'ADN/composition chimique , Sondes d'ADN/génétique , Fluorescence , Techniques de biocapteur/méthodes , Taille de particuleRÉSUMÉ
Size selectivity is crucial in highly accurate preparation of biosensors. Herein, we described an innovative electrochemiluminescence (ECL) sensing platform based on the confined DNA tetrahedral molecular sieve (DTMS) for size-selective recognition of nucleic acids and small biological molecule. Firstly, DNA template (T) was encapsulated into the inner cavity of DNA tetrahedral scaffold (DTS) and hybridized with quencher (Fc) labeled probe DNA to prepare DTMS, accordingly inducing Ru(bpy)32+ and Fc closely proximate, resulting the sensor in a "signal-off" state. Afterwards, target molecules entered the cavity of DTMS to realize the size-selective molecular recognition while prohibiting large molecules outside of the DTMS, resulting the sensor in a "signal-on" state due to the release of Fc. The rigid framework structure of DTS and the anchor of DNA probe inside the DTS effectively avoided the nuclease degradation of DNA probe, and nonspecific protein adsorption, making the sensor possess potential application prospect for size-selective molecular recognition in diagnostic analysis with high accuracy and specificity.
Sujet(s)
Techniques de biocapteur , Mesures de luminescence , Mesures de luminescence/méthodes , Photométrie , Techniques de biocapteur/méthodes , ADN , Sondes d'ADN , Techniques électrochimiques/méthodesRÉSUMÉ
Carbon nanomembranes (CNMs), with a high density of subnanometer channels, enable superior salt separation performance compared to conventional membranes. However, defects that occur during the synthesis and transfer processes impede their technical realization on a macroscopic scale. Here, we introduce a practical and scalable interfacial polymerization method to effectively heal defects while preserving the subnanometer pores within CNMs. The defect-healed freestanding CNMs show an exceptional performance in forward osmosis (FO), achieving a water flux of 105 L m-2 h-1 and a specific reverse salt flux of 0.1 g L-1 when measured with 1 M NaCl as draw solution. This water flux is 10 times higher than that of commercially available FO membranes, and the reverse salt flux is 70% lower. Through successful implementation of the defect-healing method and support optimization, we demonstrate the synthesis of fully functional, centimeter-scale CNM-based composite membranes showing high water permeance and a high salt rejection. Our defect-healing method presents a promising pathway to overcome limitations in CNM synthesis, advancing their potential for practical salt separation applications.
RÉSUMÉ
Body size is a key component of individual fitness and an important factor in the structure and functioning of populations and ecosystems. Disentangling the effects of environmental change, harvest and intra- and inter-specific trophic effects on body size remains challenging for populations in the wild. Herring in the Northwest Atlantic provide a strong basis for evaluating hypotheses related to these drivers given that they have experienced significant warming and harvest over the past century, while also having been exposed to a wide range of other selective constraints across their range. Using data on mean length-at-age 4 for the sixteen principal populations over a period of 53 cohorts (1962-2014), we fitted a series of empirical models for temporal and between-population variation in the response to changes in sea surface temperature. We find evidence for a unified cross-population response in the form of a parabolic function according to which populations in naturally warmer environments have responded more negatively to increasing temperature compared with those in colder locations. Temporal variation in residuals from this function was highly coherent among populations, further suggesting a common response to a large-scale environmental driver. The synchrony observed in this study system, despite strong differences in harvest and ecological histories among populations and over time, clearly indicates a dominant role of environmental change on size-at-age in wild populations, in contrast to commonly reported effects of fishing. This finding has important implications for the management of fisheries as it indicates that a key trait associated with population productivity may be under considerably less short-term management control than currently assumed. Our study, overall, illustrates the need for a comparative approach within species for inferences concerning the many possible effects on body size of natural and anthropogenic drivers in the wild.
Sujet(s)
Écosystème , Poissons , Animaux , Pêcheries , Température , Mensurations corporellesRÉSUMÉ
Patterned surfaces with distinct regularity and structured arrangements have attracted great interest due to their extensive promising applications. Although colloidal patterning has conventionally been used to create such surfaces, herein, we introduce a novel 3D patterned poly(N-isopropylacrylamide) (PNIPAM) surface, synthesized by using a combination of colloidal templating and surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization. In order to investigate the temperature-driven 3D morphological variations at a lower critical solution temperature (LCST) of â¼32 °C, multifaceted characterization techniques were employed. Atomic force microscopy confirmed the morphological transformations at 20 and 40 °C, while water contact angle measurements, upon heating, revealed distinct trends, offering insights into the correlation between surface wettability and topography adaptations. Moreover, quartz crystal microbalance with dissipation monitoring and electrochemical measurements were employed to detect the topographical adjustments of the unique hollow capsule structure within the LCST. Tests using different sizes of PSNPs shed light on the size-selective capture-release potential of the patterned PNIPAM, accentuating its biomimetic open-close behavior. Notably, our approach negates the necessity for expensive proteins, harnessing temperature adjustments to facilitate the noninvasive and efficient reversible capture and release of nanostructures. This advancement hopes to pave the way for future innovative cellular analysis platforms.
RÉSUMÉ
The assembly of MXene materials into microcapsules has drawn great attentions due to their unique properties. However, rational design and synthesis of MXene-based microcapsules with specific nanostructures at the molecular scale remains challenging. Herein, we report a strategy to synthesize N/P co-doped MXene hollow flower-like microcapsules with adjustable permeability via dual surfactants assisted hydrothermal-freeze drying method. In contrast to anionic surfactants, cationic surfactants exhibited effective electrostatic interactions with MXene nanosheets during the hydrothermal process. Manipulation of dual surfactants in hydrothermal process realized N and P co-doping of MXene to improve flexibility and promoted the generation of abundant internal cavities in flower-like microcapsules. Based on the unique microstructure, the prepared hollow flower-like microcapsules showed excellent performance, stability and reusability in size-selective release of small organic molecules. Moreover, the release rate can be controlled by turning the oxidation state and type of MXene. The strategy delineates promising prospects for the design of MXene-based microcapsules with specific structures.
RÉSUMÉ
The harvest of the edible sea urchin Paracentrotus lividus is intensively practiced in some regions of the Western Mediterranean Sea. The removal of the largest individuals can determine an overall reduction in population size and a size class truncation that can lead to a drastic drop the self-sustenance. The aim of this study is to evaluate the variability of the population reproductive potential across 5 years in one of the main harvest hotspots of Sardinia (Western Mediterranean Sea). The breeding stock consists of commercial and under-commercial size individuals which were sampled on a monthly basis to estimate their GonadoSomatic Index (GSI) and the Individual Gamete Output (IGO). In addition, the reproductive potential of the population-Total Gamete Output (TGO)-was calculated across the 5-year period in relation with the variation of the density of the breeding stock. During the last year, the reproductive potential was also estimated in a well-conserved population of a nearby Marine Protected Area. No significant variability in GSI and IGO was found over the 5 years nor when compared with the ones of protected population in the last year. However, the intensive harvest drastically rescaled the population body-size: although density of the commercial size class remained low, density of the under-commercial size-class halved from the beginning to the end of the study. Accordingly, the proportional decrease of their gamete output contribution led to a 40% loss of the reproductive potential of the whole population in the 5-year period. Interestingly, despite the loss of reproductive potential due to the decrease of the breeding stock density, the average values of IGO slightly increased across the years leading to the highest Annual Gamete Output (AGO) during the fourth year of sampling. This positive pattern could suggest a mechanism of reproductive investments of the survivors in terms of gonad production rate or increase in spawning intensity. This work provides evidence of the direct effect of size-selective harvesting on the rapid loss of population self-sustenance. Furthermore, it lays new prospective for future research of the indirect effects of the rescaling population body-size in functional traits of the sea urchin P. lividus and that could become important for both, sustainable exploitation and ecosystem conservation management.
Sujet(s)
Paracentrotus , Animaux , Écosystème , Italie , Densité de population , Études prospectivesRÉSUMÉ
Microplastics, as an emergent pollutant, have garnered substantial attention within aquatic environments, yet a significant knowledge gap persists regarding the interplay of organism size and pollution impacts on microplastic uptake in freshwater ecosystems. The main aim of the current study is to assess the microplastic ingestion by aquatic organisms across diverse trophic levels. To achieve this objective, zooplankton, mussels (Anodonta anatina), and fish (Carassius gibelio) were collected from the highly polluted Susurluk River Basin in Türkiye. The size distribution encompassed 160.8 ± 56.9 µm for the prevailing zooplankton, 6.9 ± 2.2 cm for mussel, and 20.4 ± 3.1 cm for fish, respectively. While no microplastic ingestion was observed among zooplankton, the finding highlights the influence of body-size and pollution on microplastic ingestion. In contrast, A. anatina and C. gibelio contained 617 and 792 microplastic particles, respectively. Predominantly, fibers emerged as the most prevalent microplastic type across trophic levels (except zooplankton) followed by films. Notably, only fish exhibited fragments within their gastrointestinal tract. A substantial correlation emerged between microplastic abundance and mussel size and weight, but no such correlation manifested for fish. The study also revealed a positive link between microplastic count and turbidity (phosphate and high Chl a level), impacting mussel ingestion capacity due to the variability in the food availability and potential shifts in feeding preferences. Conversely, no distinct pattern emerged for fish concerning water quality parameters and ingested microplastics. Consequently, our study underscores diverse microplastic uptake patterns in freshwater ecosystems, with a predominant frequency of microplastics falling with the 0.3 mm-3.0 mm range, emphasizing the significance of size-selective uptake by organisms.
RÉSUMÉ
Mechanically compliant conductors are of utmost importance for the emerging fields of soft electronics and robotics. However, the development of intrinsically deformable organic conductors remains a challenge due to the trade-off between mechanical performance and charge mobility. In this study, we report a solution to this issue based on size-selective ionic crosslinking. This rationally designed crosslinking mediated by length-regulated oligo(ethylene glycol) pendant groups and metal ions simultaneously improved the softness and toughness and ensured excellent mixed ionic-electronic conductivity in poly(3,4-ethylenedioxythiophene):polystyrene sulfonate composite materials. Moreover, the added ions remarkably promoted accumulation of charge carriers in response to temperature gradient, thus offering a viable approach to stretchable thermoelectric generators with enhanced stability against humidity.
RÉSUMÉ
In terrestrial and marine ecosystems, migrants from protected areas may buffer the risk of harvest-induced evolutionary changes in exploited populations that face strong selective harvest pressures. Understanding the mechanisms favoring genetic rescue through migration could help ensure evolutionarily sustainable harvest outside protected areas and conserve genetic diversity inside those areas. We developed a stochastic individual-based metapopulation model to evaluate the potential for migration from protected areas to mitigate the evolutionary consequences of selective harvest. We parameterized the model with detailed data from individual monitoring of two populations of bighorn sheep subjected to trophy hunting. We tracked horn length through time in a large protected and a trophy-hunted populations connected through male breeding migrations. We quantified and compared declines in horn length and rescue potential under various combinations of migration rate, hunting rate in hunted areas and temporal overlap in timing of harvest and migrations, which affects the migrants' survival and chances to breed within exploited areas. Our simulations suggest that the effects of size-selective harvest on male horn length in hunted populations can be dampened or avoided if harvest pressure is low, migration rate is substantial, and migrants leaving protected areas have a low risk of being shot. Intense size-selective harvest impacts the phenotypic and genetic diversity in horn length, and population structure through changes in proportions of large-horned males, sex ratio and age structure. When hunting pressure is high and overlaps with male migrations, effects of selective removal also emerge in the protected population, so that instead of a genetic rescue of hunted populations, our model predicts undesirable effects inside protected areas. Our results stress the importance of a landscape approach to management, to promote genetic rescue from protected areas and limit ecological and evolutionary impacts of harvest on both harvested and protected populations.
RÉSUMÉ
Non-enveloped virus-like particles (VLPs) are versatile protein nanoparticles with great potential for biopharmaceutical applications. However, conventional protein downstream processing (DSP) and platform processes are often not easily applicable due to the large size of VLPs and virus particles (VPs) in general. The application of size-selective separation techniques offers to exploit the size difference between VPs and common host-cell impurities. Moreover, size-selective separation techniques offer the potential for wide applicability across different VPs. In this work, basic principles and applications of size-selective separation techniques are reviewed to highlight their potential in DSP of VPs. Finally, specific DSP steps for non-enveloped VLPs and their subunits are reviewed as well as the potential applications and benefits of size-selective separation techniques are shown.
RÉSUMÉ
A chemically stable 2D microporous COF (PMCR-1) was synthesized via the multicomponent Povarov reaction. PMCR-1 exhibits a remarkable and long-term stable photocatalytic H2 O2 production rate (60â h) from pure and sea water under visible light. The H2 O2 production is markedly enhanced when benzyl alcohol (BA) is added as reductant, which is also due to a strong π-π interaction of BA with dangling phenyl moieties in the COF pores introduced by the multicomponent Povarov reaction. Motivated by the concomitant BA oxidation to benzaldehyde during H2 O2 formation, the photocatalytic oxidation of various organic substrates such as benzyl amine and methyl sulfide derivatives was investigated. It is shown that the well-defined micropores of PMCR-1 enable size-selective photocatalytic oxidation.
RÉSUMÉ
Over the past decades, the presence of pharmaceutical emerging contaminants in water bodies is receiving increasing attention due to the high concentration detected from wastewater effluent. Water systems contain a wide range of components coexisting together, which increases the difficulty of removing pollutants from the water. In order to achieve selective photodegradation and to enhance the photocatalytic activity of the photocatalyst on emerging contaminants, a Zr-based metal-organic framework (MOF), termed VNU-1 (VNU represents Vietnam National University) constructed with ditopic linker 1,4-bis(2-[4-carboxyphenyl]ethynyl)benzene (H2CPEB), with enlarged pore size and ameliorated optical properties, was synthesized and applied in this study. When compared to UiO-66 MOFs, which only had 30% photodegradation of sulfamethoxazole, VNU-1 had 7.5 times higher adsorption and reached 100% photodegradation in 10 min. The tailored pore size of VNU-1 resulted in size-selective properties between small-molecule antibiotics and big-molecule humic acid, and VNU-1 maintained high photodegradation performance after 5 cycles. Based on the toxicity test and the scavenger test, the products after photodegradation had no toxic effect on V. fischeri bacteria, and the superoxide radical (·O2-) and holes (h+) generated from VNU-1 dominated the photodegradation reaction. These results demonstrate that VNU-1 is a promising photocatalyst and provide a new insight for developing MOF photocatalyst to remove emerging contaminants in the wastewater systems.
RÉSUMÉ
Numerous studies have revealed that artificial light at night alters the natural patterns of light in space and time and may have various ecological impacts at different ecological levels. However, only a few studies have assessed its effect on interactions between organisms in aquatic environments, including predator-prey interactions in lakes. To fill this gap, we performed a preliminary enclosure experiment in which we compared the foraging effect of juvenile perch (Perca fluviatilis) on a natural lake zooplankton community in the absence and presence of light of high-pressure sodium (HPS) lamps mimicking artificial light emitted by a boat. The results revealed that even short-lasting exposure to HPS lamps may result in increasing fish predation, which in turn decreased the mean body size in zooplankton populations (e.g. Bosmina thersites) and affected the relative proportion between different taxa in zooplankton communities.
RÉSUMÉ
Size-selective mortality is common in fish populations and can operate either in a positive size-selective fashion by harvesting larger-than-average fish or be negatively size-selective by harvesting smaller-than-average fish. Through various mechanisms (like genetic correlations among behaviour and life-history traits or direct selection on behaviour co-varying with growth rate or size-at-maturation), size-selection can result in evolutionary changes in behavioural traits. Theory suggests that both positive and negative size-selection without additional selection on behaviour favours boldness, while evolution of shyness is possible if the largest fish are harvested. Here we examined the impact of size-selective mortality on collective boldness across ontogeny using three experimental lines of zebrafish (Danio rerio) generated through positive (large-harvested), negative (small-harvested) and random (control line) size-selective mortality for five generations and then relaxed selection for 10 generations to examine evolutionarily fixed outcomes. We measured collective risk-taking during feeding (boldness) under simulated aerial predation threat, and across four contexts in presence/absence of a cichlid. Boldness decreased across ontogeny under aerial predation threat, and the small-harvested line was consistently bolder than controls. The large and small-harvested lines showed higher behavioural plasticity as larvae and developed personality earlier compared to the controls. The large-harvested line showed increased variability and plasticity in boldness throughout ontogeny. In the presence of a live predator, fish did not differ in boldness in three contexts compared to the controls, but the large-harvested line showed reduced behavioural plasticity across contexts than controls. Our results confirmed theory by demonstrating that size-selective harvesting evolutionarily alters collective boldness and its variability and plasticity.
Sujet(s)
Comportement prédateur , Danio zébré , Animaux , Comportement animal , Mensurations corporelles , Phénotype , Prise de risque , Danio zébré/génétiqueRÉSUMÉ
Can the advantage of risk-managing life-history strategies become a disadvantage under human-induced evolution? Organisms have adapted to the variability and uncertainty of environmental conditions with a vast diversity of life-history strategies. One such evolved strategy is multiple-batch spawning, a spawning strategy common to long-lived fishes that 'hedge their bets' by distributing the risk to their offspring on a temporal and spatial scale. The fitness benefits of this spawning strategy increase with female body size, the very trait that size-selective fishing targets. By applying an empirically and theoretically motivated eco-evolutionary mechanistic model that was parameterized for Atlantic cod (Gadus morhua), we explored how fishing intensity may alter the life-history traits and fitness of fishes that are multiple-batch spawners. Our main findings are twofold; first, the risk-spreading strategy of multiple-batch spawning is not effective against fisheries selection, because the fisheries selection favours smaller fish with a lower risk-spreading effect; and second, the ecological recovery in population size does not secure evolutionary recovery in the population size structure. The beneficial risk-spreading mechanism of the batch spawning strategy highlights the importance of recovery in the size structure of overfished stocks, from which a full recovery in the population size can follow.
Sujet(s)
Gadus morhua , Chasse , Animaux , Mensurations corporelles , Femelle , Pêcheries , Humains , Densité de population , Dynamique des populationsRÉSUMÉ
Understanding the environmental fate of microplastics is essential for their risk assessment. It is essential to differentiate size classes and degradation states. Still, insights into fragmentation and degradation mechanisms of primary and secondary microplastics into micro- and nanoplastic fragments and other degradation products are limited. Here, we present an adapted NanoRelease protocol for a UV-dose-dependent assessment and size-selective quantification of the release of micro- and nanoplastic fragments down to 10 nm and demonstrate its applicability for polyamide and thermoplastic polyurethanes. The tested cryo-milled polymers do not originate from actual consumer products but are handled in industry and are therefore representative of polydisperse microplastics occurring in the environment. The protocol is suitable for various types of microplastic polymers, and the measured rates can serve to parameterize mechanistic fragmentation models. We also found that primary microplastics matched the same ranking of weathering stability as their corresponding macroplastics and that dissolved organics constitute a major rate of microplastic mass loss. The results imply that previously formed micro- and nanoplastic fragments can further degrade into water-soluble organics with measurable rates that enable modeling approaches for all environmental compartments accessible to UV light.
Sujet(s)
Microplastiques , Polluants chimiques de l'eau , Surveillance de l'environnement , Matières plastiques , Eau , Polluants chimiques de l'eau/analyseRÉSUMÉ
Metal-organic frameworks (MOFs) not only combine globally demanded renewable energy generation and environmental remediation onto a single platform but also rationalize structure-performance synergies to devise smarter materials with remarkable performance. The robust and non-interpenetrated cationic MOF exemplifies a unique bifunctional scaffold for the efficient electrochemical oxygen evolution reaction (OER) and ultrasensitive monitoring of biohazards. The microporous framework containing Brønsted acid-functionalized [Co2(µ2-OH)(CO2)2] secondary building units (SBUs) exhibits remarkable OER performance in 1 M KOH, requiring 410 mV overpotential to obtain 10 mA cm-2 anodic current density, and a low Tafel slope of 55 mV/dec with 93.1% Faradaic efficiency. Apart from the high turnover frequency and electrochemically assessable surface area, steady OER performance over 500 cycles under potentiodynamic and potentiostatic conditions result in long-term catalyst durability. The highly emissive attribute from nitrogen-rich fluorescent struts benefits the MOF in recyclable and selective fluoro-detection of three biothiols (l-cysteine, homocysteine, and glutathione) in water with a fast response time. In addition to colorimetric monitoring in the solid and solution phases, control experiments validate size-exclusive biothiol speciation through molecular-dimension-mediated pore diffusion. The role of SBUs in the OER mechanism is detailed from density functional theory-derived free energy analysis, which also validates the importance of accessible N-sites in sensing via portraying framework-analyte supramolecular interactions.
Sujet(s)
Réseaux organométalliques , Oxygène , Dioxyde de carbone , Ions , EauRÉSUMÉ
Size-selective catalysis is of key importance in the conversion of crude oil or biomass. Here, we fabricate three pillar[5]arene-integrated porous organic polymers with three-dimensional (3D) network structures using 3D cross-linkers. The resulting polymers possess a high surface-to-mass ratio and exhibit exceptional size-selective catalysis in Knoevenagel condensation reactions. In addition, a mechanistic study indicates that the size-selective catalysis is due to the host-guest interaction between pillar[5]arene and substrates. This study suggests that macrocycle-containing polymers could be a promising candidate for size-selective catalysis.