The stable complex emulsions generated during shale oil extraction pose significant challenges for oil-water separation, yet the underlying stabilization mechanisms-particularly those involving interactions between crude oil components and residual fracturing additives-remain poorly understood. Here, we systematically investigate the emulsion stabilization mechanisms and demulsification strategies for a typical shale oil produced fluid from the Shengli Oilfield. Through active components of crude oil combined with interfacial tension and dilatational rheology measurements, we demonstrate that asphaltenes are the primary determinants of emulsion stability. More importantly, we reveal a synergistic interaction between asphaltenes and the residual fracturing thickener at the oil-water interface. This synergy generates a composite interfacial film exhibiting both high elasticity (dilatational modulus up to 31.0 mN/m) and low interfacial tension (1.4 mN/m), which accounts for the exceptional stability of the field emulsion. Stratification experiments show that gravitational settling concentrates asphaltenes in the lower layer by nearly 290-fold (from 0.01 % to 2.9 %), producing a "high asphaltene, high water, high viscosity" system with dramatically enhanced stability. Based on this mechanistic understanding, we develop a blended demulsification strategy combining a tailored polyether demulsifier (Th-2) with a water clarifier (QS). This formulation achieves 97 % water separation and 99 % oil separation within 8 h at 70 degrees C, effectively overcoming the "oil separation without water separation" limitation of single demulsifiers. This work reveals a previously unrecognized asphaltene-thickener synergy that produces a high-elasticity, low-tension composite film, and demonstrates that a simple blended demulsifier (Th-2 + QS) outperforms novel synthetic alternatives in cost and scalability.
Heparin and protamine are vital biomacromolecules extensively used in clinical settings, necessitating precise monitoring of their concentrations. In this study, a novel positively charged fluorescent probe was developed, derived from an aggregation-induced emission (AIE) luminogen, tetraphenylethylene (TPE), for the detection of heparin and protamine. The probe was designed by modifying TPE with a 4-methyl-1-(3-(trimethylammonio)propyl)pyridin-1-ium bromide moiety, which imparts enhanced water solubility and long-wavelength emission. The probe (TPE-PY-N) binds electrostatically to heparin, inducing a significant “turn-on” fluorescence response. It exhibits high selectivity and sensitivity, with a limit of detection (LOD) of 10.7 ng/mL for heparin in buffer solution. Subsequently, the addition of protamine displaces the probe molecules, leading to a “turn-off” emission. The probe’s high selectivity and sensitivity position it as a promising tool for sensing heparin and protamine in buffer and highly diluted serum.
In situ detection, isolation, and enrichment of deep-sea microorganisms are pivotal for advancing deep-sea scientific research, particularly in the study of low-abundance microbial communities. This study developed an acoustically driven microfluidic fluorescence-activated cell sorting (mu FACS) device. Its dry-wet separation architecture enables unattended, automated in situ collection, detection, and enrichment of deep-sea microorganisms. The system employs ultrasonic standing waves (USSW) to achieve sheathless three-dimensional (3-D) focusing of microbial cells, coupled with laser-based detection of scattering/fluorescence signals for real-time identification and sorting. After optimizing staining protocols, high-efficiency in situ pretreatment was achieved at 4 degrees C, delivering sorting purities of 48.23 % and 85.27 % at microbial abundances of 9.43 % and 27.40 %, respectively, with a collection rate of approximately 50 %. Hydrostatic pressure test (20 MPa) and in-situ sea trials (1,350-meter depth) confirmed the engineering feasibility and environmental adaptability of mu FACS for deep-sea in situ detection and sorting, demonstrating a 4.93-fold increase in microbial abundance. This technology provides a novel tool for investigating deep-sea microbial distribution, enabling continuous in situ enrichment and high-purity sample acquisition, thereby promising to significantly enhance understanding of deep-sea ecosystems.
A highly sensitive detection system for alpha-amylase was developed via host-guest complexation between gamma- cyclodextrin and dansyl-modified diphenylalanine (FF-Dns). The host-guest inclusion of FF-Dns into the cavity of gamma- CD in a HEPES buffer solution (10 mM, pH 7.4) significantly enhanced the fluorescence intensity, and the emission wavelength gradually shifted from 558 to 535 nm. The hydrolysis of gamma- CD by the addition of alpha-amylase released FF-Dns, leading to the recovery of the fluorescence emission characteristics. Therefore, the FF-Dns/gamma-CD host-guest complexation system can serve as a platform for the sensitive detection of alpha-amylase with good selectivity against potential interference. The limit of detection (LOD) of the system was 0.004 U/mL, with a linear working range of 0-6 U/mL. The detection assay was successfully applied in 0.1 % serum, achieving an LOD of 0.017 U/mL and a linear working range of 0-10 U/mL.
The novel food composite hydrogel with delivery function consisting of shrimp powder (SP) and kappa-carrageenan (kappa-C) was constructed and used for loading apigenin (API). Binary mixtures of liquid SP and kappa-C could form gels with solid behavior. Furthermore, the addition of API increased the initial modulus of elasticity of SP/kappa-C by approximately 47.3%, as well as a 14.9% reduction in the relaxation time T23. Moreover, the O-H stretching band and the amide I band of SP/kappa-C binary gel loaded with API were blue shifted, and the XRD characteristic peak of API disappeared in SP/kappa-C/API. In addition, broken macropores and dispersed patch microstructures were presented in SP and kappa-C, whereas the SP/kappa-C and SP/kappa-C/API hydrogels were homogeneously distributed with dense mesh and solid mesh walls. Hydrophobic interactions were the main forces in the SP/kappa-C/API composite hydrogels, which were improved 1.3-fold. Furthermore, SP/kappa-C/API was extended and released to more than 55% extent during simulated intestinal colonic digestion. These results suggested that a stable and dense binary gel was formed by SP and kappa-C, which could seal and extended release effect of API to the colon.
This study systematically investigated the crucial interfacial mechanisms regulating lipid digestion using Tween surfactants with varying structural features. In vitro digestion revealed that, Tween 40/Tween 60 strongly inhibited, Tween 20/Tween 80 significantly delayed, while Tween 81/Tween 85 minimally affected lipid digestion. Tween surfactants modulated lipid digestions primarily by competing with bile salts for interfacial adsorption rather than inactivating the lipase. The emulsifiers with appropriate hydrophilic and lipophilic balance (HLB) and small critical packing parameter (CPP), like Tween 40/Tween 60, anchored to the interface and provided steric hinderance, thus inhibited the displacement by bile salts. In addition, those interfacial layers that inhibited the diffusive exchange of amphiphiles between the interface and the bulk phase, but maintained viscoelasticity through molecular conformational rearrangement or lateral molecular reorganization, could inhibit the bile salts adsorption and thus modulate lipid digestion effectively. These findings established interfacial design principles for tailored lipid digestion control in food emulsions.
In this study, we present an amphiphilic aggregation-induced emission fluorescent probe based on tetraphenylbenzene. The probe exhibited sensitive and selective detection of protamine through a "turn-on" fluorescence signal driven by electrostatic binding. A linear correlation was established between fluorescence intensity and protamine concentration in the range of 0.8-3 mu g/mL in 4-(2-hydroxyethyl)piperazine-1-ethane-sulfonic acid (HEPES) buffer, with a limit of detection (LOD) of 6.65 ng/mL. Protamine detection was successfully demonstrated in a 0.3 % serum sample. Additionally, the electrostatic probe-protamine complex was able to detect heparin owing to the strong affinity between protamine and heparin, which was confirmed through a "turn-off" fluorescence response. The probe's sensitivity and selectivity for heparin detection were validated, with an LOD of 8.83 ng/mL and a linear working range of 1.0-2.2 mu g/mL in HEPES buffer.
The development of metal-based membranes featuring hydrophilic and oleophobic properties is essential for industrial oil-water separation. Most industrial filters have a cylindrical shape to match other filter components. The modification of the cylindrical surface is much more difficult than the plane surface owing to the challenges of reaction and mass transfer on the tubular surface. To address this issue, we developed an electrochemical deposition method that enables the direct construction of a hydrophilic and underwater oleophobic coating on a cylindrical nickel foam substrate through precise mass transfer control. By optimizing the mass transfer dynamics and employing a stepwise deposition strategy, we achieved uniform functionalization on an industrial-scale cylindrical membrane with a length of 25 cm. The modified membrane exhibits an underwater-oil contact angle exceeding 140° coupled with excellent durability, chemical stability, and thermal resistance. Notably, it demonstrates high separation efficiency, reducing the oil content in water from 1500 to below 200 ppm. This work presents a scalable and reliable fabrication route for high-performance cylindrical oil-water separation membranes with significant industrial potential.
Zwitterionic materials have gained increased attention in electrochemical energy storage field for their particular structure containing both electronegative group and electropositive group, which gives rise to their strong water absorption, high salt solubility and other multifunctional properties. This review presents typical zwitterionic structures and components in electrochemical generators, influence on electrochemical performance improvement, applications in electrochemical energy storage. Moreover, the challenges and future expectations for zwitterionic materials are further elaborated. The diversified morphologies and constructions, a wide potential for application development of zwitterions can boost the energy science and technology in the near future.
Achieving multicolor, precisely tunable cluster-induced emission in nonconjugated polymers remains a considerable challenge. Herein, we present a generalizable and scalable methodology for fabricating monodisperse, color-tunable clusteroluminescence (CL) microspheres, enabling multimodal color tuning across the spectrum from blue to orange-red through precise control of monomer type and ratio, sulfonation time, and pH conditions. Density functional theory (DFT) simulations demonstrate that conformational rigidity, resulting from the synergistic combination of prevalent hydrogen-bonding interactions, short interatomic contacts, and oxygen cluster formation, significantly enhances emission efficiency, leading to dual broadband visible emissions across the 400-700 nm wavelength range. The optimized sulfonated poly(divinylbenzene-styrene-methyl methacrylate) microspheres with 30% methyl methacrylate (MMA) content (SPSMMAs-30) exhibit excellent monodispersity and strong fluorescence across 13 standard channels of flow cytometry, with fluorescence coefficient of variation (CV) values consistently below 3%, fulfilling requirements for routine flow cytometer calibration. Compared with commercial calibration microspheres, SPSMMAs-30 show significantly higher photobleaching resistance and long-term environmental stability. Significantly, this protocol enables the first kilogram-scale synthesis of CL microspheres with highly reproducible optical properties. Furthermore, SPSMMAs-30 demonstrate sensitive tetracycline detection and promising performance in multicolor anticounterfeiting applications, substantially broadening the scope of nonconjugated CL materials for biomedicine, diagnostics, and materials science.
In this study, we introduce a salt-responsive hydrogel system utilizing a sugar-derived surfactant featuring a polyhydroxy spacer in its headgroup. The inclusion of salts enhances and organizes the intermolecular hydrogen bonding within the hydrophilic region of the polyhydroxy spacer, promoting cross-linking among surfactant molecules.
A highly sensitive detection system for protamine and trypsin activity was developed using a commercially available anionic fluorescent dye, Eosin B (EB), as the probe. EB exhibited a highly sensitive colorimetric and fluorescent response for visual detection of protamine with a good selectivity over other interfering substances in the 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer (10 mM, pH 7.4). A linear relationship between the fluorescence intensity and protamine concentration was obtained ranging from 0 to10 mu g/mL with a detection limit of 29.25 ng/mL. The presence of trypsin hydrolyzed protamine, leading to the release of EB from EB-protamine complex. The fluorescence recovery of EB can monitor the trypsin activity with satisfactory selectivity and sensitivity. The introduction of a trypsin inhibitor affected the recovery of the fluorescence. Thus, this detection system supplied a method for trypsin inhibitor screening.
A highly sensitive detection platform for heparin was constructed via the utilization of a commercially available cationic fluorescent dye (cresyl violet acetate, CV) as a fluorescence probe. The electrostatic binding between CV and heparin quenched the fluorescence in 4-(2-hydroxyethyl)-1-piperazineethanesulfonic (HEPES) buffer solution (10 mM, pH 7.1). CV was highly selective towards heparin over other potential inferring substances. The detection limit of heparin detection was 5.19 ng/mL, and the linear working range was 0 ∼ 1 μg/mL in HEPES solution. In 1 % serum, the detection platform based on the fluorescence "turn-off" behavior of CV was also successfully constructed with a detection limit of 5.86 ng/mL in the linear range of 0 ∼ 0.8 μg/mL. Moreover, the CV-heparin complex was considered a potential sensor platform for the detection of protamine because of its stronger affinity for heparin and protamine.
Engineering the microenvironment of electrode surface is one of the effective means to tune the reaction pathways in CO 2 RR. In this work, we prepared copper nanofibers with conductive polypyrrole coating by polymerization of pyrrole using polyvinyl pyrrolidone (PVP) as template. As a result, the obtained copper nanofibers Cu/Cu 2+1 O/SHNC, exhibited a superhydrophobic surface, which demonstrated very high selectivity for ethanol with a Faraday efficiency (FE) of 66.5 % at −1.1 V vs reversible hydrogen electrode (RHE) in flow cell. However, the catalyst Cu/Cu 2+1 O/NC, which was prepared under the same conditions but without PVP, possessed a hydrophobic surface and exhibited high selectivity towards ethylene at the given potentials. The mechanism for switch of reaction pathways from ethylene to ethanol in CO 2 RR was studied. Incorporating pyrrolidone groups into the polymer coating results in the formation of a superhydrophobic surface. This surface weakens the hydrogen bonding interaction between interfacial water molecules and facilitates the transfer of CO 2 , thereby enhancing the local CO 2 /H 2 O ratio. The high coverage of *CO promotes the coupling of *CO and *CHO to form C 2 intermediates, and reduces the reaction energy for the formation of *CHCHOH (ethanol path) at the interface. This ensures that the reaction pathway is directed towards ethanol.
Herein, a fluorescence detection platform for protamine and trypsin activity based on a commercially available perylene-3,4,9,10-tetracarboxylic (PTC) probe has been developed. PTC could detect protamine with good selectivity and sensitivity. The complexation of PTC and protamine caused fluorescence quenching due to electrostatic binding. The detection limit was 24.3 ng/mL, with a linear working range of 0-10 mu g/mL in HEPES buffer (10 mM, pH 7.4). Protamine detection using PTC could also be conducted in 1 % fetal bovine serum solution. The addition of trypsin was able to hydrolyze protamine efficiently, disaggregating PTC and restoring the fluorescence. The PTC-protamine system could also be used to monitor trypsin activity. The hydrolysis of protamine was inhibited due to the presence of a trypsin inhibitor, leading to a decreased fluorescence recovery. The PTC-based fluorescent system could also screen trypsin inhibitor.
In recent years, there has been a growing interest in regulating lipid digestion through the construction of various interfacial structures. In the present work, a series of complex interfacial structures were designed by combining Tween 80 in the aqueous phase and lecithin in the oil phase at different concentration ratios. The emulsification properties, the roles in regulating lipid digestion, and the interfacial dilatational rheological properties of the composite emulsifying systems were characterized. The results showed that the combination of Tween 80 and lecithin at different ratios could effectively modulate the rate of lipid digestion. The polyoxyethylene chains of Tween 80 formed a network, that provided a spatial obstacle for the adsorption of bile salts and lipases. Thus, Tween 80 significantly delayed the lipid digestion. The introduction of lecithin gradually replaced Tween 80 molecules at the interface, thus providing space for the adsorption of bile salts and lipases. In addition, as the ratio of lecithin concentration to Tween 80 increased, lecithin gradually became the dominant factor in the interfacial properties. As a result, the rate of lipid digestion was accelerated. Therefore, by compounding different ratios of lecithin and Tween 80, a series of emulsions with different lipid digestion rates were obtained. This research provides a basis for rationally designing food emulsions according to specific needs.
A novel dansyl-based fluorescent probe (DG) was designed via the introduction of a dipeptide, glycyl-L-glutamine. DG showed good selectivity and sensitivity towards Cu2+ in aqueous solutions in the pH span of 6–12. The coordination of Cu2+ with the dipeptide moiety led to the fluorescent quenching of the dansyl fluorophore. The association constant value for Cu2+ was 0.78 × 104 M− 1 in a 1 to 1 stoichiometric ratio. The detection limit in HEPES buffer solution (10 mM, pH 7.4) was 1.52 µM. DG also showed strong anti-interference capability in the presence of other metal ions. It was worth noting that DG maintained the detection ability towards Cu2+ in real water samples and cell imaging, implying the potential application opportunities in complicated environments.
Amino acid surfactants derived from animal/vegetable oils and amino acids have attracted growing interest in surfactant industry. The relationship between the molecular structures of natural building blocks and the performance of the derived surfactants has become a significant subject in their application. A series of serinate surfactants with different characteristic acyls were synthesized. The specific effect of the fatty acyl structures, namely, the hydrocarbon chain length, the number of C=C bonds, and hydroxyl substituent, on the foam properties and interfacial behaviors were revealed. The serinate surfactants with long fatty acyls showed better interfacial activity and were more closely arranged at the interface, thus improving the foam stability. But the long fatty acyls also decreased the water solubility, and lead to the decreased the foamability of N-stearyl serinate surfactant. The C=C bonds in the fatty acyl improved the water solubility of the surfactants. But multiple cis C=C bonds caused the bend of hydrocarbon chains, which was unfavorable for the close arrangement of surfactant molecules, thus leading to the decrease of the foam stability. The hydroxyl group in the ricinoleoyl decreased the intermolecular van der Waals interactions and hindered the close arrangement of ricinoleoyl serinate surfactant molecules, leading to the decrease of the foam stability.
Uncontrolled ion transport and susceptible SEI films are the key factors that induce lithium dendrite growth, which hinders the development of lithium metal batteries (LMBs). Herein, a TpPa-2SO3 H covalent organic framework (COF) nanosheet adhered cellulose nanofibers (CNF) on the polypropylene separator (COF@PP) is successfully designed as a battery separator to respond to the aforementioned issues. The COF@PP displays dual-functional characteristics with the aligned nanochannels and abundant functional groups of COFs, which can simultaneously modulate ion transport and SEI film components to build robust lithium metal anodes. The Li//COF@PP//Li symmetric cell exhibits stable cycling over 800 h with low ion diffusion activation energy and fast lithium ion transport kinetics, which effectively suppresses the dendrite growth and improves the stability of Li+ plating/stripping. Moreover, The LiFePO4//Li cells with COF@PP separator deliver a high discharge capacity of 109.6 mAh g-1 even at a high current density of 3 C. And it exhibits excellent cycle stability and high capacity retention due to the robust LiF-rich SEI film induced by COFs. This COFs-based dual-functional separator promotes the practical application of lithium metal batteries.
The interfacial interactions between bovine serum albumin (BSA) with a water-soluble surfactant polyoxyethylene sorbitan monooleate (Tween 80) and an oil-soluble surfactant sorbitan monooleate (Span 80), respectively, were studied using the interfacial dilatational rheological experiments. The BSA molecules were irreversibly adsorbed at interface and formed a network with high dilatational modulus. The increasing interfacial pressure induced the transformation of BSA molecules from a compact globular to an unfolded flexible conformation, which enhanced the relaxation process. Tween 80 formed hydrophilic complexes with BSA in the aqueous phase, significantly slowing down the dynamic adsorption. In addition, Tween 80 played a dominant role at the interface due to its higher interfacial activity, thus inhibiting the interfacial performance of BSA. As BSA and Span 80 diffused towards the interface from different phases, they adsorbed rapidly at the interface and formed a mixed adsorption layer, thus exhibiting synergistic effects in decreasing the interfacial tension. However, the alternate arrangement of BSA and Span 80 at the interface disrupted the inter-protein interactions, resulting in a significant decrease in the dilatational modulus of the interfacial film. The obtained results showed that Span 80 from the oil phase and Tween 80 from the aqueous phase interacted with the protein in different ways, and thus presented distinct dynamic adsorption processes and interfacial performance. The present work provided a theoretical foundation for their practical application in food, cosmetic, and pharmaceutical industries.