RESUMEN
Many animal- and plant-pathogenic bacteria use a type III secretion system to deliver effector proteins into host cells1,2. Elucidation of how these effector proteins function in host cells is critical for understanding infectious diseases in animals and plants3-5. The widely conserved AvrE-family effectors, including DspE in Erwinia amylovora and AvrE in Pseudomonas syringae, have a central role in the pathogenesis of diverse phytopathogenic bacteria6. These conserved effectors are involved in the induction of 'water soaking' and host cell death that are conducive to bacterial multiplication in infected tissues. However, the exact biochemical functions of AvrE-family effectors have been recalcitrant to mechanistic understanding for three decades. Here we show that AvrE-family effectors fold into a ß-barrel structure that resembles bacterial porins. Expression of AvrE and DspE in Xenopus oocytes results in inward and outward currents, permeability to water and osmolarity-dependent oocyte swelling and bursting. Liposome reconstitution confirmed that the DspE channel alone is sufficient to allow the passage of small molecules such as fluorescein dye. Targeted screening of chemical blockers based on the predicted pore size (15-20 Å) of the DspE channel identified polyamidoamine dendrimers as inhibitors of the DspE/AvrE channels. Notably, polyamidoamines broadly inhibit AvrE and DspE virulence activities in Xenopus oocytes and during E. amylovora and P. syringae infections. Thus, we have unravelled the biochemical function of a centrally important family of bacterial effectors with broad conceptual and practical implications in the study of bacterial pathogenesis.
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Proteínas Bacterianas , Células Vegetales , Enfermedades de las Plantas , Porinas , Agua , Animales , Proteínas Bacterianas/química , Proteínas Bacterianas/metabolismo , Muerte Celular , Fluoresceína/metabolismo , Liposomas/metabolismo , Oocitos/metabolismo , Oocitos/microbiología , Células Vegetales/metabolismo , Células Vegetales/microbiología , Enfermedades de las Plantas/microbiología , Porinas/química , Porinas/metabolismo , Pliegue de Proteína , Soluciones/metabolismo , Agua/metabolismo , Xenopus laevis , Concentración OsmolarRESUMEN
Macromolecular crowding is the usual condition of cells. The implications of the crowded cellular environment for protein stability and folding, protein-protein interactions, and intracellular transport drive a growing interest in quantifying the effects of crowding. While the properties of crowded solutions have been extensively studied, less attention has been paid to the interaction of crowders with the cellular boundaries, i.e., membranes. However, membranes are key components of cells and most subcellular organelles, playing a central role in regulating protein channel and receptor functions by recruiting and binding charged and neutral solutes. While membrane interactions with charged solutes are dominated by electrostatic forces, here we show that significant charge-induced forces also exist between membranes and neutral solutes. Using neutron reflectometry measurements and molecular dynamics simulations of poly(ethylene glycol) (PEG) polymers of different molecular weights near charged and neutral membranes, we demonstrate the roles of surface dielectrophoresis and counterion pressure in repelling PEG from charged membrane surfaces. The resulting depletion zone is expected to have consequences for drug design and delivery, the activity of proteins near membrane surfaces, and the transport of small molecules along the membrane surface.
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Polímeros , Proteínas , Membrana Celular , Polímeros/química , Proteínas/química , Polietilenglicoles/química , Soluciones/químicaRESUMEN
Dynamic attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy at both solutions and coatings of a semicrystalline silk material derived from Bombyx mori was applied to monitor the ß-sheet conformation, which is known to correlate with silk protein crystallinity. The secondary structure-sensitive Amide I band was analyzed. Two silk protein samples were studied: native-based silk buffer fibroin (NSF) was extracted from silk glands and regenerated silk fibroin (RSF) was extracted from degummed cocoons. Solutions of both NSF and RSF at 2 mg/mL featured low initial ß-sheet contents of 5-12%, which further increased to 47-53% after 24 h. RSF and NSF solutions at 23 mg/mL also featured low initial ß-sheet contents of 9-10%, which yet only slightly increased to 16-17% after 24 h. Coatings deposited from RSF solutions showed high surface integrity (Q > 99%) after rinsing in mineralized water, enabling interfacial drug delivery applications. RSF coatings were post-treated with either formic acid (FA) or pure methanol (MeOH) vapor to showcase inducibility of crystalline domains in RSF coatings. Such coatings were loaded with the model antibiotic drugs tetracycline (TCL) and streptomycin (STRP), and the sustained release of TCL was followed in contact with (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) (HEPES) buffer. RSF/TCL coatings post-treated with formic acid (FA) vapor followed by methanol (MeOH) vapor showed a significantly lower (52%) initial burst of rather hydrophobic TCL compared to untreated RSF/TCL coatings (72%), while no such significant release difference was observed for hydrophilic STRP. This was rationalized by a specific interaction between nonpolar TCL and hydrophobic crystalline RSF domains.
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Bombyx , Fibroínas , Animales , Bombyx/química , Espectroscopía Infrarroja por Transformada de Fourier , Fibroínas/química , Conformación Proteica en Lámina beta , Liberación de Fármacos , Seda/química , Soluciones , Materiales Biocompatibles Revestidos/química , Tetraciclina/químicaRESUMEN
Dopamine (DA), a neurotransmitter, plays a crucial role in regulating motor functions and emotions and can serve as a marker for several diseases. In this study, we report a highly sensitive polydiacetylenes (PDA)-based dual-output sensor for dopamine detection in both solution and solid phases that was developed by modifying PDA liposomes with boronic acid groups at the termini. This sensor exploits the high affinity between the catechol residue of dopamine and the -B(OH)2 group of the PDA-based probe (PDA-PhBA) to form boronate ester bonds, causing a stress-induced blue-to-red color change along with a steady increase in fluorescence response at λmax 622 nm. The PDA-PhBA-based sensor displays high sensitivity toward dopamine with low limit of detection of 6.2 ppb in colorimetric analysis and 0.6 ppb in fluorimetric measurements, demonstrating its dual optical output ability. The sensor works well for adrenaline, another catecholamine, with similar efficacy. Its practical applicability was validated by the successful recovery of trace level dopamine in blood serum and real water samples. Additionally, immobilizing PDA-PhBA liposomes in sodium alginate produced PDA beads for the solid-phase detection of dopamine with an limit of detection (LOD) of 59 nM (9.0 ppb) in colorimetric detection using a smartphone for capturing images and ImageJ software for analysis.
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Dopamina , Liposomas , Polímero Poliacetilénico , Liposomas/química , Dopamina/análisis , Dopamina/sangre , Polímero Poliacetilénico/química , Límite de Detección , Colorimetría/métodos , Polímeros/química , Poliinos/química , SolucionesRESUMEN
Because hydroxypropyl cellulose (HpC) is a popular polymeric material that forms a liquid crystalline phase in solutions with various kinds of solvents, including water, it is commonly thought that HpC has a typical rod-like structure in solution. In this study, the structures of commercial HpC samples in aqueous solution with average molar substitution numbers (MS) ranging from 3.6 to 3.9 and weight-average molar masses (Mw) ranging from 36 to 740 kg mol-1 were investigated in detail. We first used multiple techniques, including standard static and dynamic light scattering (SLS and DLS), neutron and X-ray scattering experiments, and viscometric measurements, to obtain clear evidence of rod-like structures quantitatively. The dependence of excess scattering intensities for HpC samples under dilute conditions on the magnitude of the scattering vector over a wide range from 8.9 × 10-3 to 3.0 × 10 nm-1 was reasonably described by the form factor of rod particles with length (L) and diameter (d). Although the determined L value was close to the contour length (lc) calculated from the Mw values in the lower Mw range, L became obviously less than lc with increasing Mw. The radius of gyration (Rg) determined via SLS measurements was proportional to L by a factor of approximately 3.5 â¼ â12 over the Mw range examined. These observations revealed that the conformation of HpC molecules changes from an elongated single chain to a certain folded structure, maintaining the shape of the rod-shaped particles. Moreover, the Mw dependencies of the intrinsic viscosities and translational diffusion coefficients of the HpC samples resulting from DLS measurements were reasonably described with a theoretical rod-like particle model, assuming that L and d are identical to those resulting from the scattering behaviors.
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Celulosa , Agua , Celulosa/química , Celulosa/análogos & derivados , Agua/química , Soluciones , Dispersión Dinámica de Luz , Difracción de Rayos XRESUMEN
Processing cellulose from 4-methyl morpholine n-oxide (NMMO)-water solutions is a completely circular route that produces biodegradable cellulose fibers or films while recovering reusable NMMO [Guo, Y.; Cai, J.; Sun, T.; Xing, L.; Cheng, C.; Chi, K.; Xu, J.; Li, T. The purification process and side reactions in the N-methylmorpholine-N-oxide (NMMO) recovery system. Cellulose 2021, 28(12), 7609-7617]. Despite proven success in two-dimensional applications, challenges in transitioning to three-dimensional objects arise from the critical changes that cellulose undergoes during deposition, regeneration, and postregeneration stages. While emphasizing the critical diffusion-driven precipitation during regeneration, this investigation explores the influence of extrusion temperature, printing alignment, regeneration, and drying processes on interfilament fusion, bonding, shape integrity, and mechanical properties. Three distinct drying processes: ambient, vacuum, and freeze-drying were investigated. Tensile and flexural bending tests provided insight into the delamination of dried specimens. Ambient and vacuum drying enhanced the properties of specimens, while freeze-drying resulted in a more stable shape. The findings contribute to advancing the understanding of 3D-printing cellulose from NMMO solutions, addressing crucial aspects of the extrusion, regeneration, and drying stages for enhanced applications in sustainable manufacturing.
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Celulosa , Impresión Tridimensional , Agua , Celulosa/química , Agua/química , Óxidos N-Cíclicos/química , Morfolinas/química , Soluciones , Desecación/métodosRESUMEN
Regioselective modifications of cellulose using activated cellulose derivatives such as 6-halo-6-deoxycelluloses provide a convenient approach for developing sustainable products with properties tailored to specific applications. However, maintaining precise regiochemical control of substituent distribution in 6-halo-6-deoxycelluloses is challenging due to their insolubility in most common solvents and the resulting difficulties in precise structure elucidation by modern instrumental analytical techniques. Herein, an accessible NMR-based approach toward detailed characterization of 6-halo-6-deoxycelluloses, including the determination of the degrees of substitution at carbon 6 (DS6), is presented. It is shown that the direct-dissolution cellulose solvent, tetrabutylphosphonium acetate:DMSO-d6, converts 6-halo-6-deoxycelluloses to 6-monoacetylcellulose, enabling in situ solution-state NMR measurements. A range of 1D and 2D NMR experiments is used to demonstrate the quantitivity of the conversion and provide optimum dissolution conditions. In comparison with other NMR-based derivatization protocols for elucidating the structure of 6-halo-6-deoxycelluloses, the presented approach offers major advantages in terms of accuracy, speed, and simplicity of analysis, and minimal requirements for reagents or NMR instrumentation.
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Celulosa , Espectroscopía de Resonancia Magnética , Celulosa/química , Estructura Molecular , Soluciones , Solubilidad , Solventes/químicaRESUMEN
The present work describes a protocol of chemical activation, with acid catalyst, of olive endocarps to obtain acid insoluble lignin-rich materials with high capacities for the adsorption of furfural present in aqueous media. During biomass activation, factors such as acid concentration, reaction time and temperature, solid/liquid ratio and the presence of water extractives strongly affected both the surface characteristics of the treated bioadsorbents and their capacities for furfural retention (percentage increase close to 600% with respect to the crude biomass). Once a treated solid with good adsorbent properties was obtained, the optimal conditions for adsorption were found: stirring speed 80 rpm, temperature 303 K and adsorbent load 7.5 g solid/50 cm3. Kinetic study indicated the pseudo-second order model provided the best fit of the experimental data. At 303 K, the equilibrium adsorption capacities values ranged from 2.27 mg g-1 to 29.29 mg g-1, for initial furfural concentrations between 0.49 g dm-3 and 12.88 g dm-3. Freundlich model presented the best isotherm (R2 = 0.996 and SE = 4.7%) providing KF and n values of 0.115 (mg g-1) (mg dm-3)-n and 0.610, respectively. Since physical interactions predominate in the adsorption of furfural on chemically activated olive endocarps, the furfural removal process could have occurred reversibly on the heterogeneous surface of the bioadsorbents.
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Olea , Contaminantes Químicos del Agua , Termodinámica , Lignina/química , Furaldehído , Adsorción , Agua/química , Cinética , Contaminantes Químicos del Agua/química , Concentración de Iones de Hidrógeno , SolucionesRESUMEN
The ability of thermoresponsive polymers to respond to temperature with a reversible conformational change makes them promising 'smart' materials for solutions in medical and biotechnological applications. In this work, two such polymers and structural isomers were studied: poly(N-isopropyl acrylamide) (PNiPAm) and poly(2-isopropyl-2-oxazoline) (PiPOx). We compare the critical solution temperatures (CST) of these polymers in D2O and H2O in the presence of Hofmeister series salts, as results obtained under these different solvent conditions are often compared. D2O has a higher dipole moment and electronegativity than H2O, which could significantly alter the CST transition. We used two complementary methods to measure the CST, dynamic light scattering (DLS) and differential scanning calorimetry (DSC) and found that the CST decreased significantly in D2O compared to H2O. In the presence of highly concentrated kosmotropes, the CST of both polymers decreased in both solvents. The influence of the kosmotropic anions was smaller than the water isotope effect at low ionic strengths but considerably higher at physiological ionic strengths. However, the Hofmeister anion effect was quantitatively different in H2O than in D2O, with the largest relative differences observed for Cl-, where the CSTs in D2O decreased more than in H2O measured by DLS but less by DSC. PiPOx was more sensitive than PNiPAm to the presence of chaotropes. It exhibited much higher transition enthalpies and multistep transitions, especially in aqueous solutions. Our results highlight that measurements of thermoresponsive polymer properties in D2O cannot be compared directly or quantitatively to application conditions or even measurements performed in H2O.
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Polímeros , Solventes , Temperatura , Solventes/química , Polímeros/química , Rastreo Diferencial de Calorimetría , Resinas Acrílicas/química , Óxido de Deuterio/química , Agua/química , SolucionesRESUMEN
BACKGROUND: One of the important formalisms of non-equilibrium thermodynamics is Peusner network thermodynamics. The description of the energy conversion in membrane processes, i.e., the conversion of the internal energy of the system into the dissipated energy and the free energy used for the work associated with the transport of solution components, allows us to describe the relationship between these energies and the thermodynamic forces acting in the membrane system. OBJECTIVES: The aim of this study was to develop a procedure to transform the Kedem-Katchalsky equations for the transport of binary electrolytic solutions across a membrane into the Kedem-Katchalsky-Peusner equations based on Peusner network thermodynamics. The conversion of electrochemical energy to free energy in the membrane system was also determined. MATERIAL AND METHODS: The nanobiocellulose biomembranes (Biofill) were the subject of the study with experimentally determined transport parameters for aqueous NaCl solutions. The research method is the Kedem-Katchalsky-Peusner formalism for binary electrolyte solutions with introduced Peusner coefficients. RESULTS: The coefficients of the L version of the membrane transport equations and the Peusner coupling coefficients were derived as functions of NaCl concentration in the membrane. Based on these coefficients, the fluxes of internal energy of the system, energy dissipated to the surroundings and free energy related to the transport of electrolyte across the membrane were calculated and presented as functions of the osmotic and electric forces on the membrane. CONCLUSIONS: The Peusner coefficients obtained from the transformations of the coefficients of the Kedem-Katchalsky formalism for the transport of electrolyte solutions through the Biofill membrane were used to calculate the coupling coefficients of the membrane processes and the dissipative energy flux. The dissipative energy flux takes the form of a quadratic form due to the thermodynamic forces on the membrane - second degree curves are obtained. Moreover, the dissipative energy flux as a function of thermodynamic forces allowed us to examine the energy conversion in transport processes in the membrane system.
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Electrólitos , Membranas Artificiales , Termodinámica , Electrólitos/química , Soluciones/química , Modelos Químicos , Cloruro de Sodio/químicaRESUMEN
The hydrodynamic effects of macromolecular crowding inside cells are often studied inâ vitro by using polymers as crowding agents. Confinement of polymers inside cell-sized droplets has been shown to affect the diffusion of small molecules. Here we develop a method, based on digital holographic microscopy, to measure the diffusion of polystyrene microspheres that are confined within lipid vesicles containing a high concentration of solute. We apply the method to three solutes of varying complexity: sucrose, dextran, and PEG, prepared at â¼7 % (w/w). We find that diffusion inside and outside the vesicles is the same when the solute is sucrose or dextran that is prepared below the critical overlap concentration. For poly(ethylene glycol), which is present at a concentration higher than the critical overlap concentration, the diffusion of microspheres inside vesicles is slower, hinting at the potential effects of confinement on crowding agents.
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Dextranos , Microscopía , Polietilenglicoles , Polímeros , Soluciones , Lípidos , SacarosaRESUMEN
The demand to effectively treat medical wastewater has escalated with the much greater use of antiviral drugs since the COVID-19 pandemic. Forward osmosis (FO) has great potential in wastewater treatment only when appropriate draw solutes are available. Here, we synthesize a series of smart organic-inorganic polyoxomolybdates (POMs), namely, (NH4)6[Mo7O24], (PrNH3)6[Mo7O24], (iPrNH3)6[Mo7O24], and (BuNH3)6[Mo7O24], for FO to treat antiviral-drug wastewater. Influential factors of separation performance have been systematically studied by tailoring the structure, organic characteristics, and cation chain length of POMs. POMs at 0.4 M produce water fluxes ranging from 14.0 to 16.4 LMH with negligible solute losses, at least 116% higher than those of NaCl, NH4HCO3, and other draw solutes. (NH4)6[Mo7O24] creates a water flux of 11.2 LMH, increased by more than 200% compared to that of NaCl and NH4HCO3 in long-term antiviral-drug wastewater reclamation. Remarkably, the drugs treated with NH4HCO3 and NaCl are either contaminated or denatured, while those with (NH4)6[Mo7O24] remain intact. Moreover, these POMs are recovered by sunlight-assisted acidification owing to their light and pH dual sensitivity and reusability for FO. POMs prove their suitability as draw solutes and demonstrate their superiority over the commonly studied draw solutes in wastewater treatment.
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COVID-19 , Purificación del Agua , Humanos , Aguas Residuales , Cloruro de Sodio , Pandemias , Membranas Artificiales , Ósmosis , Soluciones/química , Agua/químicaRESUMEN
Modelling the removal of monovalent and divalent ions from seawater via nanofiltration is crucial for pre-treatment in seawater reverse osmosis systems. Effective separation of divalent ions through nanofiltration and allowing the permeate containing only monovalent ions to pass through the reverse osmosis system produces pure NaCl salt from the concentrate. However, the Donnan steric pore model and dielectric exclusion assume a uniformly distributed cylinder pore morphology, which is not representative of the actual membrane structure. This study analyzed the impact of membrane thickness on neutral solute removal and investigated the effect of two different methods for calculating the Peclet number on rejection rates of monovalent and divalent salts. Results show that membrane thickness has a significant effect on rejection rates, particularly for uncharged solutes in the range of 0.5-0.7 solute radius to membrane pore size ratio. Operating pressures above 10 bar favour the use of effective active layer thickness over the membrane pore size to calculate the Peclet number. At low pressures, using the effective active layer can lead to overestimation of monovalent salt rejection and underestimation of divalent salt rejection. This study highlights the importance of appropriate Peclet number calculation methods based on applied pressure when modelling membrane separation performance.
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Filtración , Membranas Artificiales , Ósmosis , Filtración/métodos , Iones , Agua de Mar , SolucionesRESUMEN
Eukaryotic cells possess numerous dynamic membrane-less organelles, RNP granules, enriched in RNA and RNA-binding proteins containing disordered regions. We demonstrate that the disordered regions of key RNP granule components and the full-length granule protein hnRNPA1 can phase separate in vitro, producing dynamic liquid droplets. Phase separation is promoted by low salt concentrations or RNA. Over time, the droplets mature to more stable states, as assessed by slowed fluorescence recovery after photobleaching and resistance to salt. Maturation often coincides with formation of fibrous structures. Different disordered domains can co-assemble into phase-separated droplets. These biophysical properties demonstrate a plausible mechanism by which interactions between disordered regions, coupled with RNA binding, could contribute to RNP granule assembly in vivo through promoting phase separation. Progression from dynamic liquids to stable fibers may be regulated to produce cellular structures with diverse physiochemical properties and functions. Misregulation could contribute to diseases involving aberrant RNA granules.
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Amiloide/química , Ribonucleoproteína Heterogénea-Nuclear Grupo A-B/química , Proteínas Intrínsecamente Desordenadas/química , Orgánulos/química , ARN/química , Amiloide/genética , Amiloide/metabolismo , Gránulos Citoplasmáticos/química , Gránulos Citoplasmáticos/metabolismo , Escherichia coli/genética , Escherichia coli/metabolismo , Recuperación de Fluorescencia tras Fotoblanqueo , Expresión Génica , Ribonucleoproteína Nuclear Heterogénea A1 , Ribonucleoproteína Heterogénea-Nuclear Grupo A-B/genética , Ribonucleoproteína Heterogénea-Nuclear Grupo A-B/metabolismo , Humanos , Proteínas Intrínsecamente Desordenadas/genética , Proteínas Intrínsecamente Desordenadas/metabolismo , Imitación Molecular , Orgánulos/metabolismo , Polietilenglicoles/química , Agregación Patológica de Proteínas/genética , Agregación Patológica de Proteínas/metabolismo , Agregación Patológica de Proteínas/patología , Unión Proteica , Estructura Terciaria de Proteína , ARN/metabolismo , Proteínas Recombinantes/química , Proteínas Recombinantes/genética , Proteínas Recombinantes/metabolismo , Cloruro de Sodio/química , SolucionesRESUMEN
We develop a multiscale simulation model for diffusion of solutes through porous triblock copolymer membranes. The approach combines two techniques: self-consistent field theory (SCFT) to predict the structure of the self-assembled, solvated membrane and on-lattice kinetic Monte Carlo (kMC) simulations to model diffusion of solutes. Solvation is simulated in SCFT by constraining the glassy membrane matrix while relaxing the brush-like membrane pore coating against the solvent. The kMC simulations capture the resulting solute spatial distribution and concentration-dependent local diffusivity in the polymer-coated pores; we parameterize the latter using particle-based simulations. We apply our approach to simulate solute diffusion through nonequilibrium morphologies of a model triblock copolymer, and we correlate diffusivity with structural descriptors of the morphologies. We also compare the model's predictions to alternative approaches based on simple lattice random walks and find our multiscale model to be more robust and systematic to parameterize. Our multiscale modeling approach is general and can be readily extended in the future to other chemistries, morphologies, and models for the local solute diffusivity and interactions with the membrane.
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Polímeros , Polímeros/química , Soluciones , Solventes/química , Difusión , Simulación por ComputadorRESUMEN
Liposomes are widely used as synthetic analogues of cell membranes and for drug delivery. Lipid-binding DNA nanostructures can modify the shape, porosity and reactivity of liposomes, mediated by cholesterol modifications. DNA nanostructures can also be designed to switch conformations by DNA strand displacement. However, the optimal conditions to facilitate stable, high-yield DNA-lipid binding while allowing controlled switching by strand displacement are not known. Here, we characterized the effect of cholesterol arrangement, DNA structure, buffer and lipid composition on DNA-lipid binding and strand displacement. We observed that binding was inhibited below pH 4, and above 200 mM NaCl or 40 mM MgCl2, was independent of lipid type, and increased with membrane cholesterol content. For simple motifs, binding yield was slightly higher for double-stranded DNA than single-stranded DNA. For larger DNA origami tiles, four to eight cholesterol modifications were optimal, while edge positions and longer spacers increased yield of lipid binding. Strand displacement achieved controlled removal of DNA tiles from membranes, but was inhibited by overhang domains, which are used to prevent cholesterol aggregation. These findings provide design guidelines for integrating strand displacement switching with lipid-binding DNA nanostructures. This paves the way for achieving dynamic control of membrane morphology, enabling broader applications in nanomedicine and biophysics.
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ADN de Cadena Simple/metabolismo , ADN/metabolismo , Liposomas/metabolismo , Fosfatidilcolinas/metabolismo , Fosfatidiletanolaminas/metabolismo , Colesterol/química , Colesterol/metabolismo , ADN/química , ADN de Cadena Simple/química , Concentración de Iones de Hidrógeno , Cinética , Liposomas/química , Cloruro de Magnesio/química , Cloruro de Magnesio/metabolismo , Nanoestructuras/química , Nanoestructuras/ultraestructura , Conformación de Ácido Nucleico , Fosfatidilcolinas/química , Fosfatidiletanolaminas/química , Cloruro de Sodio/química , Cloruro de Sodio/metabolismo , Soluciones , TermodinámicaRESUMEN
Postoperative adhesions are most common issues for almost any types of abdominal and pelvic surgery, leading to adverse consequences. Pharmacological treatments and physical barrier devices are two main approaches to address postoperative adhesions but can only alleviate or reduce adhesions to some extent. There is an urgent need for a reliable approach to completely prevent postoperative adhesions and to significantly improve the clinical outcomes, which, however, is unmet with current technologies. Here we report that by applying a viscous, cream-like yet injectable zwitterionic polymer solution to the traumatized surface, postoperative adhesion was completely and reliably prevented in three clinically relevant but increasingly challenging models in rats. The success rate of full prevention is over 93% among 42 animals tested, which is a major leap in antiadhesion performance. Clinically used Interceed film can hardly prevent the adhesion in any of these models. Unlike current antiadhesion materials serving solely as physical barriers, the "nonfouling" zwitterionic polymer functioned as a protective layer for antiadhesion applications with the inherent benefit of resisting protein/cell adhesions. The nonfouling nature of the polymer prevented the absorption of fibronectins and fibroblasts, which contribute to the initial and late-stage development of the adhesion, respectively. This is the key working mechanism that differentiated our "complete prevention" approach from current underperforming antiadhesion materials. This work implies a safe, effective, and convenient way to fully prevent postoperative adhesions suffered by current surgical patients.
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Acrilamidas/administración & dosificación , Enfermedades Peritoneales/prevención & control , Polímeros/administración & dosificación , Complicaciones Posoperatorias/prevención & control , Procedimientos Quirúrgicos Operativos/efectos adversos , Animales , Modelos Animales de Enfermedad , Humanos , Cuidados Intraoperatorios/métodos , Enfermedades Peritoneales/etiología , Complicaciones Posoperatorias/etiología , Ratas , Soluciones , Adherencias Tisulares/etiología , Adherencias Tisulares/prevención & controlRESUMEN
Bioadhesives such as tissue adhesives, hemostatic agents, and tissue sealants have potential advantages over sutures and staples for wound closure, hemostasis, and integration of implantable devices onto wet tissues. However, existing bioadhesives display several limitations including slow adhesion formation, weak bonding, low biocompatibility, poor mechanical match with tissues, and/or lack of triggerable benign detachment. Here, we report a bioadhesive that can form instant tough adhesion on various wet dynamic tissues and can be benignly detached from the adhered tissues on demand with a biocompatible triggering solution. The adhesion of the bioadhesive relies on the removal of interfacial water from the tissue surface, followed by physical and covalent cross-linking with the tissue surface. The triggerable detachment of the bioadhesive results from the cleavage of bioadhesive's cross-links with the tissue surface by the triggering solution. After it is adhered to wet tissues, the bioadhesive becomes a tough hydrogel with mechanical compliance and stretchability comparable with those of soft tissues. We validate in vivo biocompatibility of the bioadhesive and the triggering solution in a rat model and demonstrate potential applications of the bioadhesive with triggerable benign detachment in ex vivo porcine models.
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Materiales Biocompatibles/química , Hidrogeles/química , Herida Quirúrgica/terapia , Adhesivos Tisulares/química , Adhesividad , Animales , Reactivos de Enlaces Cruzados/química , Modelos Animales de Enfermedad , Femenino , Ensayo de Materiales , Ratas , Bicarbonato de Sodio/química , Soluciones , Succinimidas/química , Porcinos , Técnicas de Cierre de Heridas/instrumentaciónRESUMEN
Here, we report a new version of the extended Rate Constants Distribution (RCD) model for metal ion sorption, which includes complex-formation equilibria. With the RCD-complex model, one can predict sorbent performance in the presence of complexing agents using data on metal ion sorption from ligand-free solutions and a set of coefficients for sorption rate constants of different ionic species. The RCD-complex model was applied to breakthrough curves of Cu(II) sorption from acetate and tartrate solutions on polyethyleneimine (PEI) monolith cryogel at different flow rates and ionic speciation. We have shown that, despite the lower stability of Cu(II)-acetate complex, at high flow rates, acetate has a more pronounced negative effect on sorption kinetics than tartrate. The RCD model was successfully used to predict the shape of the breakthrough curves at an arbitrary acetate concentration but failed to predict Cu(II) sorption from tartrate solutions in a broad range of ligand concentrations. Since a twofold increase in sorption capacity was observed at low tartrate concentrations, the latter fact was related to an alteration in the sorption mechanism of Cu(II)-ions, which depended on Cu(II) ionic speciation. The obtained results emphasize the importance of information about sorption kinetics of different ionic forms for the optimization of sorption filter performance in the presence of complexing agents.
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Criogeles , Polietileneimina , Cinética , Tartratos , Concentración de Iones de Hidrógeno , Metales , Iones , Acetatos , Adsorción , Cobre , SolucionesRESUMEN
Sustainable water recovery and reuse are critical yet challenging, especially from industrial effluents in cold regions. This work presents a robust numerical model of the transport phenomena in a hybrid two-step forward osmosis (FO)-directional freeze crystallization (DFC) desalination process, whose application in areas with cold climates is advantageous. Deionized (DI) water and a hydrometallurgical effluent were considered as the feed solution in the FO step, while three aqueous solutions of inorganic salts were considered as the draw solutions (DS): NaCl, CaCl2, and MgCl2. The effects of temperature and initial DS concentration were investigated on water flux, reverse solute flux, and specific water flux using computational fluid dynamics (CFD). Based on the simulation results, the highest water flux (18 L/m2/h for DI water and 5 L/m2/h for the hydrometallurgical effluent) and lowest reverse solute flux (consistently below 0.3 mol/m2/h) were obtained when MgCl2 was used as the DS. The effect of solute type in the DS on both water recovery yield and purity was in turn studied in the subsequent DFC step, allowing to visualize the solute distribution during the freezing process.