Amphiphilic Surfactant Research Articles

Chemotherapeutic Drug Delivery Nanoplatform Development: From Physicochemical to Preclinical Evaluation.

Through this study, the synergistic behavior of small-molecular-weight, amphiphilic surfactant molecules and the triblock copolymer Pluronic 188 was extensively evaluated based on their ability to formulate nanocarriers with novel properties for the delivery of class II and IV (biopharmaceutical classification system) chemotherapeutic compounds. The combination of four different surfactants at multiple weight ratios and twelve initially formulated nanosystems resulted in four hybrid delivery platforms, which were further studied in terms of multiple physicochemical characteristics, as well as their stability in protein-rich media (fetal bovine serum/phosphate-buffer saline). Finally, we obtained a single final nanoformulation that exhibited a high loading capacity (%EE ≥ 75%) and a sustained drug release profile under physiological conditions (model drug methotrexate), without altering the original physicochemical characteristics of the carrier. With a mean hydrodynamic radius (Rh) of less than 70 nm, a polydispersity index of 0.219, and no protein complexation, the system is a suitable candidate for in vivo, intravenous, and/or intramuscular administration. The cytotoxicity and genotoxicity of both loaded and unloaded carriers were evaluated through the examination of the upregulation or downregulation of apoptosis-related pathways. Multiple conventional 2D and 3D spheroidal conformations were used for these assessments, including HEK293, HCT-116, and MCF-7 cell lines, the results of which stressed the safety and biocompatibility of the empty nanocarrier. Additionally, experiments on Caenorhabditis elegans were conducted to evaluate the system's in vivo toxicity, focusing on developmental stages, egg-laying behavior, and locomotion. Nanosystems studied in terms of chemotherapeutic encapsulation have mostly focused on the physiochemical aspect of the development of such novel delivery platforms, with only few exceptions proceeding step-by-step from cellular 2D to 3D to in vivo experimentation. The present study offers a holistic view of the behavior of such a novel system, advancing our understanding of the capabilities of polymeric/surfactant-based nanodelivery platforms.

Responsive release of guest aqueous droplet in liquid crystal droplet assists the detection of organophosphorus using commercial pregnancy test strip

Here, we report a liquid crystal (LC) double-emulsion based system for organophosphorus (OPs) sensing by controllable release of guest aqueous droplets (GADs) cargo. First, double liquid crystal emulsion, water in liquid crystal in water (W/LC/W), with size between 4∼ 20 μm was prepared with GADs loaded at the center of liquid crystal droplet (LCD) through elasticity trap. The LCDs were monodispersed and response sensitively to amphiphilic surfactant with opposite charge. With the capability of ejecting GADs with human chorionic gonadotropin (hCG) as cargo located in LCD to continuous aqueous phase, responsive vehicles are obtained and applied in the repurposing of commercial pregnancy test strip (PTS). With hydrophobic alkyl chain and hydrophilic head, myristoylcholine (Myr) is a good amphiphilic surfactant to trigger the release of hCG, and substrate for the enzymatic hydrolysis of acetylcholine esterase (AChE). Provided with the inhibition effect of OPs to the hydrolysis ability of AChE, OPs correlate positively with the concentration of Myr, thus correlate well with the release of hCG in W/LC/W emulsion. Thus, OPs residue in river or food is readily visualized using commercial PTS.

Choline Oxidase and Choline Ionic Liquids in Biocatalytic Heme Peroxidase Cascades

Choline oxidase from Alcaligenes sp. (ChOx) is used to generate hydrogen peroxide in situ from choline‐based ionic liquids (ILs) to fuel peroxidase‐mediated biocatalysis, while mitigating oxidative degradation of the heme‐dependent enzymes. Horseradish peroxidase (HRP) and chloroperoxidase from Caldariomyces fumago (CPO), in combination with the ChOx, are evaluated in enzymatic cascades for the ability of the biocatalytic systems to withstand elevated concentrations of different choline additives in oxidative and halogenative enzymatic assays. The findings are applied in various synthetic scenarios to produce important oxygen‐ and nitrogen‐containing heterocycles, using choline ILs in a dual‐purpose fashion, as a substrate‐solubilizing component in the reaction medium as well as the source for hydrogen peroxide. The ChOx/HRP couple is used to induce intramolecular cyclizations of hydroxamic acids and hydroxycarbamates in a nitroso‐ene‐type pathway with choline dihydrogen phosphate as IL additive. The ChOx/CPO cascade successfully mediates brominative cyclizations of α‐allenic alcohols, while amphiphilic surfactants are employed to turn the aqueous choline propionate IL media into a colloidal suspension. ChOx/CPO partnering is also evaluated in an oxygenative rearrangement of 1‐furylethanol with choline acetate IL. The results show the wide potential of choline oxidase for hydrogen peroxide‐driven biocatalysis with both aqueous and micellar choline ionic liquid solutions.

Endocytosis-Inspired Zwitterionic Gel Tape for High-Efficient and Sustainable Underoil Adhesion.

Marine oil exploration is important yet greatly increases the risk of oil leakage, which will result in severe environment pollution and economic losses. It is an urgent need to develop effective underoil adhesives. However, realizing underoil adhesion is even harder than those underwater, due to the stubborn attachment of a highly viscous oil layer on target surface. Here, inspired by endocytosis, a tough gel tape composed of zwitterionic polymer network and zwitterionic surfactants is developed. The amphiphilic surfactants can form micelle to capture the oil droplets and transport them from the interface to gel via electrostatic attraction of polymer backbone, mimicking the endocytosis and achieving robust underoil adhesion. Benefiting from the oil-resistance of polymer backbone, the gel further realizes a combination of i) long-term adhesion with high durability, ii) repeated adhesion in oil, and iii) renewable adhesion efficiency after exhausted use. The tape exhibits an ultra-high adhesive toughness of 2446.86 J m-2 to stainless steel in silicone oil after 30 days' oil-exposure; such value of adhesive toughness surpasses many of those achieved in underwater adhesion and is greater than underoil adhesion performance of commercial tape. The strategy illustrated here will motivate the design of sustainable and efficient adhesives for wet environments.

Dandelion inspired microparticles with highly efficient drug delivery to deep lung

Active pharmaceutical ingredient (API) embedded dry powder for inhalation (AeDPI) shows higher drug loading and delivery dose for directly treating various lung infections. Inspired by the dandelion, we propose a novel kind of AeDPI microparticle structure fabricated by spray freeze drying technology, which would potentially enhance the alveoli deposition efficiency. When inhaling, such microparticles are expected to be easily broken-up into fragments containing API that acts as ‘seed’ and could be delivered to alveoli aided by the low density ‘pappus’ composed of excipient. Herein, itraconazole (ITZ), a first-line drug for treating pulmonary aspergillosis, was selected as model API. TPGS, an amphiphilic surfactant, was used to achieve stable primary ITZ nanocrystal (INc) suspensions for spray freeze drying. A series of microparticles were prepared, and the dandelion-like structure was successfully achieved. The effects of feed liquid compositions and freezing parameters on the microparticle size, morphology, surface energy, crystal properties and in vitro aerosol performance were systematically investigated. The optimal sample (SF(-50)D-INc7Leu3-2) in one-way experiment showed the highest fine particle fraction of ∼ 68.96 % and extra fine particle fraction of ∼ 36.87 %, equivalently ∼ 4.60 mg and ∼ 2.46 mg could reach the lung and alveoli, respectively, when inhaling 10 mg dry powders. The response surface methodology (RSM) analysis provided the optimized design space for fabricating microparticles with higher deep lung deposition performance. This study demonstrates the advantages of AeDPI microparticle with dandelion-like structure on promoting the delivery efficiency of high-dose drug to the deep lung.

Artificial magnetosomes: Molecularly restructured SPIONs with enhanced potential for magnetic imaging

Magnetosomes represent an elegant example of ultrastable nanomaterials that nature produces by encapsulating magnetic nanoparticles in liposomal sub-compartments of magnetotactic bacteria. Materials chemists continue to strive for ways to mimic the performance of natural systems, but the artificial synthesis of magnetosomes remains unrealized. Here, we report molecular restructuring of the surface of oleic-acid-capped superparamagnetic iron oxide nanoparticles (SPIONs) to produce magnetosomes. Our strategy involves the use of triethylamine as an amphiphilic surfactant that through a combination of ligand exchange and rearrangement mechanisms, facilitates an organic-to-aqueous phase transfer of SPIONs while turning them into magnetosomes. These liposome-encapsulated SPIONs showed dynamic aqueous stability alongside noticeably improved magnetic properties. This improved their performance as contrast agents for magnetic resonance imaging (MRI) and magnetic particle imaging (MPI), the latter revealing a 33.5 % improvement in signal sensitivity over the original SPIONs. The presented strategy is extendable to prepare liposomal dispersions of other biomedically important nanomaterials.

Partitioning of an Enzyme-Polymer Surfactant Nanocomplex into Lipid-Rich Cellular Compartments Drives In Situ Hydrolysis of Organophosphates.

Most organophosphates (OPs) are hydrophobic, and after exposure, can sequester into lipophilic regions within the body, such as adipose tissue, resulting in long term chronic effects. Consequently, there is an urgent need for therapeutic agents that can decontaminate OPs in these hydrophobic regions. Accordingly, an enzyme-polymer surfactant nanocomplex is designed and tested comprising chemically supercharged phosphotriesterase (Agrobacterium radiobacter; arPTE) electrostatically conjugated to amphiphilic polymer surfactant chains ([cat.arPTE][S-]). Experimentally-derived structural data are combined with molecular dynamics (MD) simulations to provide atomic level detail on conformational ensembles of the nanocomplex using dielectric constants relevant to aqueous and lipidic microenvironments. These show the formation of a compact admicelle pseudophase surfactant corona under aqueous conditions, which reconfigures to yield an extended conformation at a low dielectric constant, providing insight into the mechanism underpinning cell membrane binding. Significantly, it demonstrated that [cat.arPTE][S-] spontaneously binds to human mesenchymal stem cell membranes (hMSCs), resulting in on-cell OP hydrolysis. Moreover, the nanoconstruct can endocytose and partition into the intracellular fatty vacuoles of adipocytes and hydrolyze sequestered OP.

Robust superhydrophobic Poly(vinylidene fluoride) membranes with spherulitic surface morphology against wetting and scaling in membrane distillation

Membrane distillation (MD) offers a theoretically complete interception of salts, presenting a promising desalination pathway for freshwater supply. However, conventional hydrophobic membranes fail to desalinate water containing surfactants or supersaturated gypsum over prolonged periods. To address wetting and scaling challenges, we developed a superhydrophobization methodology for poly (vinylidene fluoride) membranes by in situ controlling spherulitic surface morphology through thermally induced phase separation. The major advantages of this one-step strategy lie in its fluorination-free, template-free, and nanoparticle-free. The as-prepared membranes exhibit a rough morphology and superhydrophobic characters with high air-trapping pockets. They demonstrate stable vapor fluxes and high salt rejections (>99 %) when used in desalination processes for saline water containing 0.6 mM sodium dodecyl sulfate, 0.03 mM cetyltrimethylammonium bromide, or gypsum solution with a saturation index of 1.1. Also, the outstanding anti-wetting and anti-scaling properties were demonstrated using synthetic shale gas wastewater. The formation of an air layer on the integrated spherulitic surface highlights the local kinetic barrier and slippery surface, effectively preventing the attachment of amphiphilic surfactants and mineral ions. Importantly, due to the membrane's structural integrity, the spherulitic surface displays high robustness and minimal impact from abrasion cycles and ultrasonication. This work exemplifies a facile strategy to engineer micro-/nano-spherulitic surface morphology for robust superhydrophobic membranes used in MD desalination.

The Role of Amphiphilic Nanosilica Fluid in Reducing Viscosity in Heavy Oil

Heavy oil accounts for a considerable proportion of the world’s petroleum resources, and its exploitation helps to mitigate reliance on conventional oil resources and diversify energy supply. However, due to the high viscosity and high adhesion characteristics of heavy oil, conventional methods such as thermal recovery, emulsification, and dilution have significant limitations and cannot meet the growing demands for heavy oil production. In this study, 3-propyltrimethoxysilane (MPS) was used to modify and graft amphiphilic surfactants (AS) onto nanosilica to prepare a salt-resistant (total mineralization > 8000 mg/L, Ca2+ + Mg2+ > 1000 mg/L) and temperature-resistant (250 °C) nanosilicon viscosity reducer (NSD). This article compares amphiphilic surfactants (AS) as conventional viscosity-reducing agents with NSD. FTIR and TEM measurements indicated successful bonding of 3-propyltrimethoxysilane to the surface of silica. Experimental results show that at a concentration of 0.2 wt% and a mineralization of 8829 mg/L, the viscosity reduction rates of thick oil (LD-1) before and after aging were 85.29% and 81.36%, respectively, from an initial viscosity of 38,700 mPa·s. Contact angle experiments demonstrated that 0.2 wt% concentration of NSD could change the surface of reservoir rock from oil-wet to water-wet. Interfacial tension experiments showed that the interfacial tension between 0.2 wt% NSD and heavy oil was 0.076 mN/m. Additionally, when the liquid-to-solid ratio was 10:1, the dynamic and static adsorption amounts of 0.2 wt% NSD were 1.328 mg/g-sand and 0.745 mg/g-sand, respectively. Furthermore, one-dimensional displacement experiments verified the oil recovery performance of NSD at different concentrations (0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%) at 250 °C and compared the oil recovery efficiency of 0.2 wt% NSD with different types of demulsifiers. Experimental results indicate that the recovery rate increased with the increase in NSD concentration, and 0.2 wt% NSD could improve the recovery rate of heavy oil by 22.8% at 250 °C. The study of nano-demulsification oil recovery systems can effectively improve the development efficiency of heavy oil.

Synchronized Codelivery of Combination Chemotherapies Intratumorally Using a Lipidic Lyotropic Liquid Crystal System.

In this work, an injectable in situ depot-forming lipidic lyotropic liquid crystal (L3C) system is developed to codeliver a precisely synchronized combination of chemotherapeutics intratumorally. The developed L3C system is composed of amphiphilic lipids and surfactants, including monoolein, phosphatidylcholine, tocopherol acetate, and d-α-tocopherol polyethylene glycol 1000 succinate. Owing to its amphiphilic nature, the developed formulation can coaccommodate both hydrophobic and hydrophilic chemotherapeutic moieties simultaneously. The study presents a proof of concept by designing a combination chemotherapy regimen in vitro and demonstrating its in vivo translation using doxorubicin and paclitaxel as model hydrophilic and hydrophobic drug moieties, respectively. The synchronized combination of the two chemotherapeutics with maximum synergistic activity was identified, coloaded in the developed L3C system at predefined stoichiometric ratios, and evaluated for antitumor efficacy in the 4T1 breast tumor model in BALB/c mice. The drug-loaded L3C formulation is a low-viscosity injectable fluid with a lamellar phase that transforms into a hexagonal mesophase depot system upon intratumoral injection. The drug-loaded depot system locally provides sustained intratumoral delivery of the chemotherapeutics combination at their precisely synchronized ratio for over a period of one month. Results demonstrate that the exposure of the tumor to the precisely synchronized intratumoral chemotherapeutics combination via the developed L3C system resulted in significantly higher antitumor activity and reduced cardiotoxicity compared to the unsynchronized combination chemotherapy or the synchronized but uncoordinated drug delivery administered by a conventional intravenous route. These findings demonstrate the potential of the developed L3C system for achieving synchronized codelivery of the chemotherapeutics combination intratumorally and improving the efficacy of combination chemotherapy.

Comparing an Integrated Amphiphilic Surfactant to Traditional Hydrophilic Coatings for the Reduction of Catheter-Associated Urethral Microtrauma.

Hydrophilic-coated intermittent catheters have improved the experience of intermittent urinary catheterization for patients compared to conventional gel-lubricated uncoated catheters. However, the incorporation of polyvinylpyrrolidone (PVP) within hydrophilic coatings can lead to significant issues with coating dry-out. Consequently, increased force on catheter withdrawal may cause complications, including urethral microtrauma and pain. Standard methods of evaluating catheter lubricity lack physiological relevance and an understanding of the surface interaction with the urethra. The tribological performance and urethral interaction of commercially available hydrophilic PVP-coated catheters and a coating-free integrated amphiphilic surfactant (IAS) catheter were evaluated by using a biomimetic urethral model designed from a modified coefficient of friction (CoF) assay. T24 human urothelial cells were cultured on customized silicone sheets as an alternate countersurface for CoF testing. Hydrophilic PVP-coated and coating-free IAS catheters were hydrated and the CoF obtained immediately following hydration, or after 2 min, mimicking in vivo indwell time for urine drainage. The model was observed for urethral epithelial cell damage postcatheterization. The majority of hydrophilic PVP-coated catheters caused significantly greater removal of cells from the monolayer after 2 min indwell time, compared to the IAS catheter. Hydrophilic PVP-coated catheters were shown to cause more cell damage than the coating-free IAS catheter. A biomimetic urethral model provides a more physiologically relevant model for understanding the factors that govern the frictional interface between a catheter surface and urethral tissue. From these findings, the use of coating-free IAS catheters instead of hydrophilic PVP-coated catheters may help reduce urethral microtrauma experienced during catheter withdrawal from the bladder, which may lead to a lower risk of infection.

Supramolecular confinement effect enabling light-harvesting system for photocatalytic α-oxyamination reaction

The supramolecular Förster resonance energy transfer (FRET) is seen as a promising approach for organic photocatalysis using dyes as catalysts, because it combines the high efficiency of energy transfer with the dynamic responsiveness based on non-covalent interactions. Here we propose a supramolecular FRET photocatalysis strategy for α-oxyamination reaction based on supramolecular confinement effect. The well-designed benzothiadiazole-based cationic monomer as energy donor and the dyes of Nile Red as acceptor are doped into the amphiphilic surfactants of sodium dodecyl sulfate (SDS). Benefitting from the supramolecular confinement space provided by SDS in aqueous environment, the FRET process between the monomer and Nile Red is effectively achieved (exciton migration rate: 3.99 × 1014 L mol‒1 s‒1). On this basis, the supramolecular FRET system is used as an efficient energy source to catalyze α-oxyamination reactions between a series of 1,3-dicarbonyl compounds and 2,2,6,6-tetramethylpiperidine-1-oxyl under white LED light, showing a yield as high as 94 % and a turnover frequency value of 3.92 h‒1. This photocatalytic result shows a great enhancement compared to that of Nile Red alone.

Exploiting Ascorbyl Palmitate Assisted-Chondroitin Sulfate /Chitosan Nanoparticles for Intra-articular Delivery of Lipoic Acid

The objective of this study was to explore the anti-arthritic potential of lipoic acid (LA) with antioxidant and anti-inflammatory effects via developing nanoparticles (NPs) based on chitosan (CH) and chondroitin sulfate (CS). The impact of the auxiliary amphiphilic non-surfactant; ascorbyl palmitate (AP) was investigated on the colloidal parameters of CH based NPs and compared with the commonly utilized amphiphilic surfactant; lecithin (L). The proposed nanoparticles (CS/CH NPs) were characterized for colloidal properties (particle size and zeta potential), entrapment efficiency, morphology, physical state of LA and its interaction with the polymeric matrix, in vitro release and antioxidant potential. Adjuvant-induced arthritic model in rats was established and the histopathological states of knee joints were checked. Joint tissue homogenate levels of tumor necrosis factor-α (TNF-α), interleukin-10 (IL-10), superoxide dismutase (SOD) and malondialdehyde (MDA) were also determined. The prepared NPs containing AP (AP-CS/CH NPS) with a positive surface charge showed significantly reduced particle size and higher LA entrapment relative to those containing L (261.22 nm versus 304.62 nm and 70.65% versus 65.10%). For LA loaded AP-CS/CH NPS, sustained LA release over 1-week period and substantial antioxidant potential were verified. The in vivo results revealed that the proposed NPs exhibited higher inhibition of inflammation than those lacking AP (51.04% versus 35.88% at the 21st day of treatment respectively) with a down-regulation of TNF-α and up-regulation of IL-10. An appreciable boost in SOD and a decline in MDA levels were also detected. Thus, the developed LA loaded nanoformulation could be a promising candidate in anti-arthritis therapy.

Glutaminolysis inhibition boosts photodynamic therapy to eliminate cancer stem cells

High reactive oxygen species (ROS) levels provide a therapeutic opportunity to eradicate cancer stem cells (CSCs), a population of cells responsible for tumorigenesis, progression, metastasis, and recurrence. However, enhanced antioxidant systems in this population of cells attenuate ROS-inducing therapies. Here, we developed a nanoparticle-assisted combination therapy to eliminate CSCs by employing photodynamic therapy (PDT) to yield ROS while disrupting ROS defense with glutaminolysis inhibition. Specifically, we leveraged an oleic acid-hemicyanine conjugate (CyOA) as photosensitizer, a new entity molecule HYL001 as glutaminolysis inhibitor, and a biocompatible folic acid-hydroxyethyl starch conjugate (FA-HES) as amphiphilic surfactant to construct cellular and mitochondrial hierarchical targeting nanomedicine (COHF NPs). COHF NPs inhibited glutaminolysis to reduce intracellular ROS scavengers, including glutathione (GSH) and nicotinamide adenine dinucleotide phosphate (NADPH), and to blunt oxidative phosphorylation (OXPHOS) for oxygen-conserved PDT. Compared to COLF NPs without glutaminolysis inhibitor, COHF NPs exhibited higher phototoxicity to breast cancer stem cells (BCSCs) both in vitro and in vivo. More importantly, we corroborated that marketed glutaminolysis inhibitors, such as CB839 and V9302, augment the clinically used photosensitizer (Hiporfin) for BCSCs elimination. This study develops a potent CSCs targeting strategy by combining glutaminolysis inhibition with PDT and provides significant implications for cancer therapy.

Surfactant‐Templated Synthesis of High‐Performance Noble Metal Electrocatalysts: A Case of Dioctadecyldimethylammonium Chloride

Mesoscopic structures of noble metal (NM) nanomaterials are important parameters that remarkably affect physicochemical properties and electrocatalytic performances. To date, various synthesis strategies have been proposed to prepare NM nanomaterials with well‐defined mesoscopic structures. Specifically, amphiphilic surfactants that chemically composed of hydrophobic tail(s) and hydrophilic head(s) have been utilized as functional templates to precisely engineer mesoscopic structures of NM nanomaterials and further optimize their electrochemical performance. Compared with traditional surfactants, dioctadecyldimethylammonium chloride (DODAC) is a functional amphiphilic surfactant that can assemble into vesical and cylinder micelles and thus template precise synthesis of NM nanomaterials with various advanced structures. In this review, recent developments in DODAC‐templated synthesis of high‐performance NM electrocatalysts with a specific focus on the findings in the group are presented. Three kinds of advanced NM mesoscopic structures, including one‐dimensional (1D) nanowires, three‐dimensional (3D) mesoporous nanospheres (MSs), and sophisticated hollow/asymmetric MSs, are described in detail. Meanwhile, the applications in various electrocatalytic reactions are presented to highlight high activity, selectivity, and stability of NM electrocatalysts. This review provides some insights into both synthesis and application exploration of high‐performance NM electrocatalysts by templated synthesis of amphiphilic surfactants.

A theragenerative bio-nanocomposite consisting of black phosphorus quantum dots for bone cancer therapy and regeneration

Recently, the term theragenerative has been proposed for biomaterials capable of inducing therapeutic approaches followed by repairing/regenerating the tissue/organ. This study is focused on the design of a new theragenerative nanocomposite composed of an amphiphilic non-ionic surfactant (Pluronic F127), bioactive glass (BG), and black phosphorus (BP). The nanocomposite was prepared through a two-step synthetic strategy, including a microwave treatment that turned BP nanosheets (BPNS) into quantum dots (BPQDs) with 5 ± 2 nm dimensions in situ. The effects of surfactant and microwave treatment were assessed in vitro: the surfactant distributes the ions homogenously throughout the composite and the microwave treatment chemically stabilizes the composite. The presence of BP enhanced bioactivity and promoted calcium phosphate formation in simulated body fluid. The inherent anticancer activity of BP-containing nanocomposites was tested against osteosarcoma cells in vitro, finding that 150 μg mL−1 was the lowest concentration which prevented the proliferation of SAOS-2 cells, while the counterpart without BP did not affect the cell growth rate. Moreover, the apoptosis pathways were evaluated and a mechanism of action was proposed. NIR irradiation was applied to induce further proliferation suppression on SAOS-2 cells through hyperthermia. The inhibitory effects of bare BP nanomaterials and nanocomposites on the migration and invasion of bone cancer, breast cancer, and prostate cancer cells were assessed in vitro to determine the anticancer potential of nanomaterials against primary and secondary bone cancers. The regenerative behavior of the nanocomposites was tested with healthy osteoblasts and human mesenchymal stem cells; the BPQDs-incorporated nanocomposite significantly promoted the proliferation of osteoblast cells and induced the osteogenic differentiation of stem cells. This study introduces a new multifunctional theragenerative platform with promising potential for simultaneous bone cancer therapy and regeneration.

Switching Product Selectivity in Immobilized Tungstate Catalysts by Control of Hydrophobicity of Mesoporous Silicate Supports

AbstractNovel mesoporous silicates modified with imidazolium cation were applied as the support for peroxotungstate. Stepwise introduction of multiple functional groups to SBA‐15 was achieved by the combination of the direct and post‐synthesis procedures. The co‐condensation of tetraethoxysilane and 3‐(imidazolyl‐1‐yl)‐propyltriethoxysilane in the presence of the micelles of an amphiphilic surfactant yields the hydrophilic SBA‐15 type silicate support with the imidazole modifier locating into the mesopores. The hydrophobic environment of the supports was imparted by capping the residual silanols on the silicate surface with trimethylsilyl groups. The fluoroalkyl‐ or alkyl‐imidazolium cation‐anchored supports were derived from the corresponding imidazole‐functionalized precursors. The anion‐exchanging reaction between peroxytungstate and the imidazolium cation‐anchored supports yielded the corresponding tungstate‐immobilized catalysts. The hydrophilic catalyst with the fluoroalkyl‐imidazolium mediated alkene epoxidation with H2O2 in less polar solvents. The hydrophobic one, in contrast, produced diol through the epoxidation and following hydration in an aqueous solvent by the action of the highly Lewis acidic tungsten. The hydrophobic catalysts had the advantage of being more tolerant than hydrophilic catalysts, as evidenced by reusability tests. The activities of the alkyl‐imidazolium catalysts were lower than those of the corresponding fluoroalkyl‐imidazolium catalysts, indicating that the local structures surrounding the tungstate site affected the catalytic performance.

Nanocellulose‐Based Ink for Vertically 3D Printing Micro‐Architectures with High‐Resolution

AbstractNanocellulose has become an important renewable component for composite inks, owing to its desirable physical properties, reinforcing capabilities, and tunable self‐assembly behavior. However, it is difficult to improve the rheological performance of the nanocellulose‐based composite to meet the requirement for 3D printing high resolution microarchitectures. Herein, a strategy is proposed that incorporation of amphiphilic molecular surfactant into nanocellulose gel can increase the molecular interaction via hydrophobic bonds and enhance the ink viscoelasticity. Following the design, a composite ink is formulated by adding xylan and Nonaethylene glycol monododecyl ether (C12E9) within nanocellulose gel. A new printing program is designed to achieve vertical writing of the composite ink and obtain free‐standing micropillars and microhemispheres with high resolution in dozens of micrometers. The microhemisphere on an atomic force microscope (AFM) cantilever can be used as colloidal probe. This work proves that nanocellulose composite ink is a candidate for 3D printing functional devices with special microstructures.

Enhanced hydrogen sequestration through hydrogen foam generation with SDS Co-Injection in subsurface formations

Inherent obstacles of hydrogen injection encompass preferential channeling through larger pathways, hampering microscopic sweep efficiency within porous media. This work pioneers hydrogen foam generation via co-injection with aqueous sodium dodecyl sulfate (SDS) to enhance subsurface hydrogen trapping capacity. SDS addition substantially reduces hydrogen-water interfacial tension and enhances viscoelasticity. In contrast to robust hydrogen foam stability, CO2 foams display compromised integrity, stemming from surfactant aggregation and ensuing infiltration channels that permit aqueous phase CO2 dissolution. Hydrogen foams conversely sustain uniform surfactant films, forestalling hydrogen ingress into water. Synergetic microfluidic and pore-scale simulations visualise mechanisms underlying intensified hydrogen capture and mobility reduction attributed to deformation and flow resistance when traversing constricted pores. Introducing the amphiphilic SDS surfactant considerably promotes hydrogen adsorption through its hydrophobic tail. Core flooding experiments quantify over 2 times hydrogen storage ratio amplification with SDS relative to sole hydrogen injection. The framework contributes pragmatic strategies to harness high-efficiency hydrogen foam for scalable clean energy storage.

Surfactant-assisted interfacial polymerization towards high-crystallinity COF membranes for organic solvent nanofiltration

Preparing high-crystallinity covalent organic framework (COF) membranes by interfacial polymerization remains a grand challenge. Herein, a monomer pre-assembly process is proposed to prepare high-crystallinity COF membranes by surfactant-assisted interfacial polymerization (SAIP) strategy. The self-assembled chains of amphiphilic surfactants across interface can gather and pre-assemble monomers and improve their interphase transport for complete topological growth. Apart from the reduction in polymerization time from over 72 h–48 h, the crystallinity and pore uniformity of COF membranes are highly enhanced. This strategy is universal and four kinds of amine monomers are utilized to tune COF pore size. The 1.8 nm-sized COF membrane shows highly enhanced rejection from 65.5% to 95.7% for reactive black with a size of 2.0 nm, when compared to that without surfactants. Importantly, the orderly stacked pores permit fast molecule transport with a 76% increase in acetonitrile permeance (366.9 L m−2 h−1 bar−1). Meanwhile, the robust crystal properties endow this COF membrane with excellent solvent resistance, compressive strength, and hence operational stability for over 100 h. The amphiphilic molecule-assisted interface engineering may represent a technology for scalable fabrication of high-crystallinity framework materials for molecule separation.