Ethylene Oxide Research Articles

Constructing efficient lithium salt dissociation solid-state electrolytes with high conductivity and transference number of Li ions for stable all-solid-state lithium batteries

The broad application of solid-state polymer electrolytes (SPEs) has been hindered by the extremely low transference number of lithium ions and ionic conductivities. This study innovatively introduces Co-doped Li4Ti5O12 (CLTO) into poly(ethylene oxide) (PEO) matrix, CLTO not only brings a stronger interaction with TFSI−, but also weakens the Li-O bond in Li4Ti5O12 and reduces the diffusion activation energy of Li+. Thus, CLTO introducing PEO-based polymer solid electrolytes could simultaneously promote the dissociation of Li+ from LiTFSI and Li4Ti5O12, constructing efficient dual lithium salt dissociation regions and rapid Li+ conduction channels. The experimental tests and density functional theory calculations have confirmed the operational mechanisms of CLTO within the polymer matrix. As a result, the obtained SPEs exhibit a high ionic conductivity (1.09 × 10−4 S cm−1) and a quite large tLi+ of 0.83 at 60 °C. Moreover, the low (Highest Occupied Molecular Orbital) HOMO energy (−7.25 eV) of the CLTO-LiTFSI-PEO-10 (CLP-10) endow it can accommodate both the Li-metal anode and high-voltage cathodes. The all-solid-state LiFePO4||Li and NCM811|| Li batteries offer exceptional specific capacities of 164.61 and 194.95 mAh/g at 60 °C, respectively. In addition, the pouch cell assembled with CLP-10 works stably under extreme conditions such as bending and shearing.

Demulsification of steam-assisted gravity drainage (SAGD) emulsions under high temperature and high pressure: Effects of emulsion breaker and reverse emulsion breaker dosages

Effective treatment of complex emulsions formed during steam-assisted gravity drainage (SAGD) production is crucial for oil/water separation and subsequent processing. However, it remains challenging due to the complexity of SAGD emulsions, and there are only very limited studies on demulsification under simulated SAGD conditions. This study systematically characterized the comprehensive properties of a fresh field SAGD emulsion with about 84.6 % water and 15.4 % bitumen, and then achieved effective demulsification under a simulated SAGD condition at 135 °C and 60 psi via adding a poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) copolymer (as a model emulsion breaker or EB) combined with a branched polyethylenimine (PEI, as a model reverse emulsion breaker or REB) in a bench-scale bottle test setup. The effects of EB and REB dosages on the demulsification of the SAGD emulsion were evaluated based on the properties of the separated phases. Dynamic interfacial tension, zeta potential, and coalescence time were measured to reveal the demulsification mechanisms of EB and REB. The highly interface-active EB facilitated oil dehydration by displacing the natural interface-active species at the interfaces, disrupting the rigid interfacial films and promoting water droplet coalescence, while the cationic REB aided water de-oiling by neutralizing oil droplet surface charge, disrupting the rigid interfacial films and promoting the approach and coalescence of oil droplets in aqueous media. This work has improved the understanding of SAGD emulsion characteristics, the effects of EB and REB dosages on the demulsification performance, and the underlying demulsification mechanisms in SAGD operations. The results provide useful insights for developing effective and cost-efficient chemical approaches to address challenging emulsion issues in oil production.

Simultaneous process optimization and heat integration for ethylene-to-ethylene oxide process: A surrogate model-based approach

Since the production process of ethylene to ethylene oxide (EO) is highly energy-intensive, it is necessary to perform a whole process heat integration. However, due to the technical barriers, it is always a challenge to design the heat integration system while optimizing the process parameters by mechanistic models. In response to this issue, this study presented a novel surrogate model-based framework that allows for the seamless integration of process optimization and heat exchanger network (HEN) design. The EO production process is modeled and simulated to provide the essential data for surrogate model training. Considering the inherent complexity of the process and the challenges associated with model training, the whole production process is decomposed into parts and the output parameters relevant to heat integration are included within the surrogate models training by Artificial Neural Network. Building upon these preliminary steps, a flexible optimization framework built upon the Genetic Algorithm, integrating the developed process surrogate model and any HEN synthesis model, is constructed to achieve synchronous optimization. The results show that the obtained process saves 22.93 % utility cost and finally leads to a 2.60 % increase in total profit than the alternative designed by the conventional stepwise method, showing the priority of the proposed method.

Effect of ethylene oxide groups on calcite wettability reversal by nonionic surfactants: An experimental and molecular dynamics simulation investigation

HypothesisEthoxylated nonionic surfactants are promising candidates for enhanced oil recovery (EOR) from oil-wet carbonate reservoirs due to their ability to reverse the mineral wettability. The wettability-reversal efficiency increases with the number of the ethoxy (EO) groups in the surfactant molecule. MethodologyContact angle measurements, scanning electron microscopy (SEM) and molecular dynamics (MD) simulations were combined to investigate the wettability reversal of an oil-wet calcite by three ethoxylated nonionic surfactants with 1, 4 and 8 EO groups, respectively, to directly probe the role of the EO groups and to uncover the molecular mechanism responsible for the wettability reversal. FindingsBoth experiments and simulations consistently show a clear correlation between the number of EO groups and the wettability reversal efficiency of the surfactants, whereby the higher number of EO groups results in greater degree of wettability reversal. This is due to 1) the more hydrophilic surfactant headgroup weakening the carboxylate interactions with the surface by expanding the surface-adjacent water layer, and 2) the physically larger surfactant molecule attracting the carboxylates more strongly, thus aiding in their removal from the surface.

Dual Contributions of Analyte Adsorption and Electroosmotic Inhomogeneity to Separation Efficiency in Capillary Electrophoresis of Proteins.

Improving separation efficiency in capillary electrophoresis (CE) requires systematic study of the influence of the electric field (or solute linear velocity) on plate height for a better understanding of the critical parameters controlling peak broadening. Even for poly(diallyldimethylammonium chloride) (PDADMAC)/poly(sodium styrenesulfonate) (PSS) successive multiple ionic-polymer layer (SMIL) coatings, which lead to efficient and reproducible separations of proteins, plate height increases with migration velocity, limiting the use of high electric fields in CE. Solute adsorption onto the capillary wall was generally considered as the main source of peak dispersion, explaining this plate height increase. However, experiments done with Taylor dispersion analysis and CE in the same conditions indicate that other phenomena may come into play. Protein adsorption with slow kinetics and few adsorption sites was established as a source of peak broadening for specific proteins. Surface charge inhomogeneity was also identified as a contribution to plate height due to local electroosmotic fluctuations. A model was proposed and applied to partial PDADMAC/poly(ethylene oxide) capillary coatings as well as PDADMAC/PSS SMIL coatings. Atomic force microscopy with topography and recognition imaging enabled the determination of roughness and charge distribution of the PDADMAC/PSS SMIL surface.

Ethylene oxide hemoglobin adducts in cord blood and offspring’s size at birth: The NewGeneris European Cohort Study

Ethylene oxide hemoglobin adducts in cord blood and offspring’s size at birth: The NewGeneris European Cohort Study

Stability of Li1.3Al0.3Ti1.7(PO4)3-Based Composite Electrolytes against Lithium Anodes Enhanced by Uniform Surface Coating of Two-Dimensional Graphene-like C3N4 on Particle Surfaces.

All-solid-state lithium (Li) batteries have attracted considerable interest due to their potential in high energy density as well as safety. However, the realization of a stable Li/solid-state electrolyte (SSE) interface remains challenging. Herein, two-dimensional graphene-like C3N4 (g-C3N4) as a coating layer on Li1.3Al0.3Ti1.7(PO4)3 (LATP) electrolyte (LATP@CN) has been applied to construct the stable Li/SSE interface. The g-C3N4 layer is uniformly coated on the LATP surface using the in situ calcination method, which not only enhances the dispersibility of LATP particles in poly(ethylene oxide) (PEO) through the interaction between surface functional groups but also suppresses the side reactions between Li and LATP. The coating layer can effectively improve the interfacial stability. As a result, the conductivity and stability of the obtained composite solid-state electrolytes (CSEs) against Li are enhanced. The Li∥CSEs∥Li symmetric cells stably cycle for 670 and 600 h at 0.1 and 0.2 mA cm-2, respectively. The Li∥CSEs∥LiFePO4 cells stably cycle more than 100 times at 0.1 and 0.2 C with a capacity retention rate of about 86% and 88%, respectively. This work inspires a new strategy to avoid the reactions between LATP and Li.

Stable Cycling of All-Solid-State Lithium Batteries Enabled by Cyano-Molecular Diamond Improved Polymer Electrolytes

HighlightsAdditive of 1-adamantanecarbonitrile is used to strengthen the poly(ethylene oxide) based solid polymer electrolytes (SPEs).LiF-based integral cathode/SPE and Li/SPE interfaces are generated.The NMC811/Li all-solid-state performs stable cycle at 45 °C (1000, 80%).

Robust and Adhesive Laminar Solid Electrolyte with Homogenous and Fast Li-Ion Conduction for High-Performance All-Solid-State Lithium Metal Battery.

Constructing composite solid electrolytes (CSEs) integrating the merits of inorganic and organic components is a promising approach to developing high-performance all-solid-state lithium metal batteries (ASSLMBs). CSEs are now capable of achieving homogeneous and fast Li-ion flux, but how to escape the trade-off between mechanical modulus and adhesion is still a challenge. Herein, a strategy to address this issue is proposed, that is, intercalating highly conductive, homogeneous, and viscous-fluid ionic conductors into robust coordination laminar framework to construct laminar solid electrolyte with homogeneous and fast Li-ion conduction (LSE-HFC). A 9µm-thick LSH-HFC, in which poly(ethylene oxide)/succinonitrile is adsorbed by coordination laminar framework with metal-organic framework nanosheets as building blocks, is used here as an example to determine the validity. The Li-ion transfer mechanism is verified and works across the entire LSE-HFC, which facilitates homogeneous Li-ion flux and low migration energy barriers, endowing LSE-HFC with high ionic conductivity of 5.62×10-4Scm-1 and Li-ion transference number of 0.78 at 25°C. Combining the outstanding mechanical strength against punctures and the enhanced adhesion force with electrodes, LSE-HFC harvests uniform Li plating/stripping behavior. These enable the realization of high-energy-density ASSLMBs with excellent cycling stability when being assembled as LiFePO4/Li and LiNi0.6Mn0.2Co0.2O2/Li cells.

Rapid-Response Water-Shrink Films with High Output Work Density Based on Polyethylene Oxide and α-Cyclodextrin for Autonomous Wound Closure.

Conventional wound closure methods, including sutures and tissue adhesives, present significant challenges for self-care treatment, particularly in the context of bleeding wounds. Existing stimuli-responsive contractile materials designed for autonomous wound closure frequently lack sufficient output work density to generate the force needed to bring the wound edges into proximity or necessitate stimuli that are not compatible with the human body. Here, semi-transparent, flexible, and water-responsive shrinkable films, composed of poly(ethylene oxide) and α-cyclodextrin, are reported. These films exhibit remarkable stability under ambient conditions and demonstrate significant contraction (≈50%) within 6 s upon exposure to water, generating substantial contractile stress (up to 6MPa) and output work density (≈1028kJ m-3), which is 100 times larger than that of conventional hydrogel and 25 times larger than that of skeletal muscles. Remarkably, upon hydration, these films are capable of lifting objects 10000 times their own weight. Leveraging this technology, water-shrink tapes, which, upon contact with water, effectively constrict human skin and autonomously close bleeding wounds in animal models within 10 seconds, are developed further. This work offers a novel approach to skin wound management, showing significant potential for emergency and self-care scenarios.

Catalytic Hydroxyethylation of Phenols with Renewable Ethylene Glycol Diester as an Alternative to Ethylene Oxide

AbstractPolyol esters are abundant bio‐based resources. Integration of polyol esters into the production chain of fine chemicals would reduce carbon emissions and improve the sustainability of the chemical industry. An efficient synthetic route to phenoxyethanols was developed through catalytic hydroxyethylation of phenols with ethylene glycol diacetate as the reagent. This method showed the potential of ethylene glycol diester as a safe and sustainable substitute for ethylene oxide, a useful but toxic reagent. A variety of phenoxyethanol esters were produced in high yield under simple catalytic conditions. Mechanistic studies revealed that the reaction underwent a neighboring group participation process.

Mechanical properties of co-continuous network polymers packed with thiol-ene thermosets in epoxy monolith

Co-continuous network polymers (CNPs) as the new polymer composites are fabricated by filling the continuous pores of an epoxy monolith with a high glass transition temperature (Tg) using another kind of network polymer with a low Tg. In this study, we prepared sheet-like and cylindrical CNPs using thiol–ene thermosets as the second component with a low Tg. A thiol–ene reaction is suitable for the preparation of thermosets with a controlled network structure. Here, various thiols and acrylates including the different numbers of functional groups and/or oligo(ethylene oxide) spacers with different lengths are used for the fabrication of the second thermosetting component. We investigated the tensile and compression mechanical properties of the produced CNPs. Dynamic mechanical analysis (DMA) of the thiol–ene bulk thermosets (BTs) as the second component was also carried out in order to clarify the influence of the Tg and the crosslinking density on the mechanical and physical properties of the CNPs. The results of the mechanical tests were discussed on the functionality of the used acrylate and thiol compounds. In conclusion, we have revealed that the properties of CNPs are not only dependent on the crosslinking density, but also significantly affected by the detailed network structure of the second component.

Coal-Based Branched Vicinal Diol Ethoxylates Versus Guerbet Alcohol Ethoxylates: Role of Tertiary Hydroxyl Groups.

Branched surfactants exhibit a lower surface tension, excellent low defoaming performance, and better wetting ability compared with linear surfactants, making them promising for applications in industrial cleaning. In this study, 2-hexyl-1-decene (C8 olefin dimer), obtained from the dimerization of 1-octene, was used as the hydrophobe to synthesize branched nonionic surfactants via hydroxylation and ethoxylation. The hydroxylation of the C8 olefin dimer to synthesize 2-hexyldecane-1,2-diol (C8 BD) using H2O2 and HCOOH was investigated systematically. Under the optimal reaction conditions (H2O2/C8 olefin dimer molar ratio: 1.5, HCOOH/C8 olefin dimer molar ratio: 4.0, reaction time: 10 h, reaction temperature: 50 °C), the conversion of the C8 olefin dimer and selectivity toward C8 BD were found to reach 99.96 and 79.89%, respectively. Further, branched nonionic surfactants (C8 BDEn) were synthesized via ethoxylation of C8 BD with ethylene oxide and characterized using FTIR, LCMS, 1H NMR, and 13C NMR techniques. The presence of a tertiary hydroxyl group in C8 BD increases the reactivity of the primary hydroxyl group, leading to a narrower range of products and lower residual substrate content. The physicochemical properties and surface properties of C8 BDEn with different degrees of ethoxylation at various concentrations were investigated and compared with those of commercially available Guerbet alcohol polyoxyethylene ethers (C8 GAEO9 and C6 GAEO9). The results show that, compared with C8 GAEO9 and C6 GAEO9, C8 BDE6 displayed a higher surface activity with a lower equilibrium surface tension (27.14 mN·m-1), superior wettability with a smaller contact angle (39.2°), better emulsification performance with a longer emulsification time of 548 s, and excellent foaming properties (initial foam volume of 11.6 mL). This strategy of utilizing coal-based α-olefins for the synthesis of branched nonionic surfactants presents a route to prepare value-added fine chemicals from coal-based resources.

Contact Angle Modulation: In Situ Polymer Deposition during Sessile Drop Evaporation.

The drying kinetics of a sessile drop on a solid surface are a widely studied phenomenon because of their relevance to various fields such as coating, printing, medical diagnostics, sensing, and microfluidic technology. Typically, the drop undergoes drying either at a constant contact radius (R) with a decrease in the three-phase contact angle or at a constant contact angle (θ) with a reduction in the radius with time. These two drying modes are referred to as CCR and CCA, respectively. It is not uncommon where both R and θ may decrease during drying, especially in the penultimate stage of drying. In this work, we report a scenario wherein the θ increases while R decreases during the drying process of an aqueous polymer solution on a high surface energy substrate. This behavior is observed across different polymer systems (such as poly(ethylene oxide) and polyvinyl pyrrolidine), varying molecular weights, and polymer concentrations. As the drop dries, the polymer gets deposited at the three-phase contact line, thus reducing the surface energy of the substrate and leading to an increase in the contact angle. The drop responds by attempting to reach a new equilibrium contact angle through slipping. The temporal increase in contact angle follows a power law scaling behavior. This study demonstrates an in situ modulation of contact angle facilitated by evaporation and polymer deposition, showcasing unconventional drying dynamics.

High-Strength, Thin, and Lightweight Solid Polymer Electrolyte for Superior All-Solid-State Sodium Metal Batteries.

The utilization of solid polymer electrolytes (SPEs) in all-solid-state sodium metal batteries has been extensively explored due to their excellent flexibility, processability adaptability to match roll-to-roll manufacturing processes, and good interfacial contact with a high-capacity Na anode; however, SPEs are still impeded by their inadequate mechanical strength, excessive thickness, and poor stability with Na anodes. Herein, a robust, thin, and cost-effective polyethylene (PE) film is employed as a skeleton for infiltrating poly(ethylene oxide)-sodium bis(trifluoromethanesulfonyl)imide (PEO/NaTFSI) to fabricate PE-PEO/NaTFSI SPE. The resulting SPE features a remarkable thickness of 25 μm, lightweight property (2.1 mg cm-2), superior mechanical strength (tensile strength = 100.3 MPa), and good flexibility. The SPE also shows an ionic conductivity of 9.4 × 10-5 S cm-1 at 60 °C and enhanced interfacial stability with a sodium metal anode. Benefiting from these advantages, the assembled Na-Na symmetric cells with PE-PEO/NaTFSI show a high critical current density (1 mA cm-2) and excellent long-term cycling stability (3000 h at 0.3 mA cm-2). The all-solid-state Na||PE-PEO/NaTFSI||Na3V2(PO4)3 coin cells exhibit a superior cycling performance, retaining 93% of the initial capacity for 190 cycles when matched with a 6 mg cm-2 cathode loading. Meanwhile, the pouch cell can work stably after abuse testing, proving its flexibility and safety. This work offers a promising strategy to simultaneously achieve thin, high-strength, and safe solid-state electrolytes for all-solid-state sodium metal batteries.

Hybrid Single Crystals of Poly(ε‐caprolactone) Homopolymers and Poly(ε‐caprolactone)‐b‐Poly(ethylene oxide) Block Copolymers

AbstractHybrid single crystals (HSCs) of different poly(ε‐caprolactone) (PCL) homopolymers with a poly(ε‐caprolactone)‐b‐poly(ethylene oxide) (PCL‐b‐PEO) block copolymer (BCP) are prepared. The effects of PCL length, PCL/PCL‐b‐PEO molar ratio, crystallization temperature (Tc), and solvent on crystal morphology are investigated. The optimal Tc for the formation of more perfect HSCs is between those for homocrystals of individual PCL and PCL‐b‐PEO and roughly increases with the length of PCL and PCL/PCL‐b‐PEO molar ratio. The chain folding in the HSCs is studied by comparing the experimentally measured heights obtained by atomic force microscopy (AFM) and theoretically calculated ones based on a sandwich structure model. Under most situations, the PCL homopolymers adopt a larger chain folding number in the HSCs than that in their homocrystals, while the chain folding of BCP remains unaltered. However, when both PCL homopolymer and PCL‐b‐PEO BCP crystallize slowly and the overcrowding of the PEO is effectively alleviated, thicker HSCs can be formed, in which the PCL homopolymer preserves the chain folding in its homocrystals but the BCP adopts a reduced chain folding number as compared with that in its homocrystals. The relative crystallization rate of PCL homopolymer versus BCP also affects the real composition and overall height of the HSCs.

Molecular dynamics study of free volume coalescence around nonyl ethoxylate in polyethylene with vinyl acetate‐modified branches

AbstractPolyethylene (PE) is susceptible to environmental stress cracking (ESC). In the presence of an amphiphilic compound and subjected to stress, ESC starts with cavitation followed by slow crack growth and ends with brittle fracture. In this study, we used molecular dynamics simulation to study how branch ends which were chemically modified with vinyl acetate groups affect free volume coalescence around an amphiphilic compound, nonyl ethoxylate (NE), dispersed in branched PE models. Branch ends modified with vinyl acetate significantly impact the free volume coalescence dynamics around NE. Compared with methyl branch ends, vinyl acetate branch ends show a much higher affinity, as quantified by the corresponding radial distribution functions, for the hydrophilic ethylene oxide‐segment of NE. However, this is not the case for the hydrophobic ethylene‐segment. Interestingly, vinyl acetate branch ends tend to reduce the power (amplitude) of the free volume size fluctuations around both the ethylene oxide‐ and ethylene‐segments. Indeed, the powers of the fluctuations with different PE branching characteristics decrease with increasing vinyl acetate concentration. We believe that free volume coalescence leads to cavitation and that vinyl acetate branches could inhibit cavitation, thereby crack propagation in PE. The power results seem to be consistent with the experimental observation that the addition of copolymer ethylene vinyl acetate to low‐density polyethylene improves the ESC resistance of the blend.Highlights Vinyl acetate branches reduce free volume coalescence activities. Vinyl acetate branches are attracted to the hydrophilic segment of NE. Cavitation likely starts from the free volume coalescence around NE.

A highly flexible and adhesive polymer electrolyte with fast ion conduction prepared via UV-induced in-situ polymerization for lithium metal batteries

Cathode–electrolyte integration via in-situ polymerization is an effective strategy to reduce interfacial resistance in solid-state/quasi-solid-state lithium batteries; however, ion conduction in the fraction of polymer electrolyte is still to be enhanced. Herein, we demonstrate a separator-free cathode–electrolyte integrated structure employing a novel poly(di(ethylene glycol) ethyl ether acrylate)-based quasi-solid polymer electrolyte (LiTFSI-poly(DEGA)-FEC QSPE, denoted as PDEGA-QSPE), prepared via UV-assisted in-situ polymerization. Poly(DEGA) as a linear polymer contains abundant ethylene oxide (EO) segments in its branched chain, exhibiting excellent flexibility and high adhesion. Benefited from the flexible molecular structure, PDEGA-QSPE exhibits a glass transition temperature (Tg) as low as around −68 °C and a good room-temperature ionic conductivity of 2.3 × 10−4 S cm−1, and it also shows an oxidative potential up to 4.7 V. The LiFePO4|PDEGA-QSPE|Li battery possesses an initial capacity of 149.2 mAh g−1 and a capacity retention of 92.5 % after 300 cycles at 0.2C under room temperature, and poly(DEGA)-based QSPE also has the potential to be applied to the high-voltage NCM811||Li battery. Compared with widely-employed monomers for in-situ polymerization such as poly(ethylene glycol) diacrylate (PEGDA), poly(DEGA) possesses remarkably improved flexibility and ion conduction capability, exhibiting broad research and application prospects.

A Proteomic Approach to Determine Stem Cell Skeletal Differentiation Signature on Additive Manufactured Scaffolds

Understanding how porous biomaterials interact with cells at their surface and how they either promote or inhibit cellular processes has presented several challenges. Additive manufacturing enables the fabrication of scaffolds with distinct compositions and designs for different tissue engineering applications. To evaluate the in vitro performance of multiple printed materials, biochemical assays can be limiting in providing valuable insight and key information to select the best tissue destination. Omics technologies like proteomics are crucial for studying important cellular events and gathering valuable information about cellular processes and mechanisms. However, only few studies focus on proteomics to decipher cell–material interactions and cell differentiation on additive manufactured scaffolds. Here, scaffolds were fabricated using three polymers (polycaprolactone (PCL), poly(ethylene oxide)–poly(butylene terephthalate) (PEOT/PBT), and polylactic acid (PLA)) through additive manufacturing. Their chondrogenic and osteogenic potential were characterized and compared using human bone marrow‐derived mesenchymal stem cells (hBMSCs) through proteomics analysis. The 3D scaffolds were all hydrophilic and displayed Young's moduli close to those of bone or cartilage for PLA and PCL and PEOT/PBT, respectively. Biochemical assays indicated that PEOT/PBT and PLA scaffolds have a greater chondrogenic potential by higher glycosaminoglycan (GAG) and collagen deposition compared to PCL. PLA and PEOT/PBT showed to be more effective in promoting bone formation, as evidenced by higher calcium deposits detected by alizarin red staining, and higher alkaline phosphatase (ALP), especially for PLA in osteogenic medium. Proteomics data revealed the most distinct separation between conditions in chondrogenic medium, which had the highest protein identification rates. Pathway analysis showed that PCL did not induce any differentiation‐related pathways when compared to PEOT/PBT and PLA in any of the tested media conditions. Analysis of PEOT/PBT proteins showed pathways involved in chondrogenesis in all three media and pathways related to hypertrophic phenotype progression in chondrogenic medium. These data suggests that PEOT/PBT is a valuable candidate for cartilage and osteochondral applications, able to drive hBMSCs differentiation without the need of growth factors. PLA was also a valuable candidate for cartilage and bone applications by upregulating both chondrogenic and osteogenic‐related proteins in maintenance and chondrogenic media. In osteogenic and maintenance media, the upregulation of angiogenic proteins makes PLA a better candidate for bone application where vascularization is key.

The role of chlorine promoters in mediating particle size effects in silver-catalyzed ethylene epoxidation

Measured chlorine coverages over Ag/α-Al2O3 catalysts with varying Ag weight loadings (1.3–35 wt%) and different Ag particle size distributions when parsed in terms of Cl coverages over particles of varying size constituted in the distribution reveal that Ag particles of size below ∼30 nm are covered in more than 1 monolayer (ML) of chlorine in presence of 3.5 ppm C2H5Cl. These assessments of Cl coverages were made possible by correlating the cumulative Cl coverage to the lognormal surface area distribution of 22 Ag/α-Al2O3 samples using a single exponential decay function. Fully chlorided small Ag particles exhibit low rates of epoxidation and only large Ag particles which exhibit sub-monolayer Cl coverages catalyze ethylene epoxidation with high ethylene oxide (EO) rates and selectivity. The Ag particle size dependence of Cl coverages plausibly explains why ≥ 100 nm Ag particles are typical in promoted Ag/α-Al2O3 ethylene epoxidation catalysts.