Hydrophobic Alkyl Chains Research Articles

Van der Waals interactions between nonpolar alkyl chains and polar oxide surfaces prevent catalyst deactivation in aldehyde gas sensing

Catalysis-based electrical sensing of volatile organic compounds on metal oxide surfaces is a powerful method for molecular discrimination. However, catalyst deactivation caused by the poisoning of catalytic sites by analytes and/or catalyzed products remains a challenge. This study highlights the underestimated role of van der Waals interactions between hydrophobic aliphatic alkyl chains and hydrophilic ZnO surfaces in mitigating catalyst deactivation during aliphatic aldehyde sensing. By immobilizing octadecylphosphonic acid (ODPA) on ZnO nanowire sensors, recovery times for nonanal detection are significantly reduced without compromising sensitivity. Temperature-programmed measurements demonstrate a reduction in desorption temperature of carboxylates on ODPA-modified ZnO to below 150 °C, whereas carboxylates on bare ZnO remain above 300 °C, indicating a significant decrease in catalyst deactivation. Density functional theory calculations reveal that accumulated van der Waals interactions between alkyl chains and ZnO surfaces significantly contributed to adsorption molecular kinetics. IR spectroscopy using deuterated self-assembled monolayers (SAMs) reveals conformational changes of alkyl chains within the SAMs caused by aldehyde adsorption, supporting the suggested adsorption kinetics. A model is proposed based on the dynamic surface-covering by alkyl chains destabilizes catalytically oxidized carboxylic acids.

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.

Combinatorial Synthesis of Alkyl Chain-Capped Poly(β-Amino Ester)s for Effective siRNA Delivery.

Poly (β-amino ester) (PBAE) is a class of biodegradable polymers containing ester bonds in their main chain, extensively investigated as cationic polymer carriers for siRNA. Most current PBAE carriers rely on termination with hydrophilic or charged amines. In this study, a polymer platform consisting of 168 PBAE polymers with hydrophobic alkyl chain terminals is constructed through sequential aza-Michael addition. A large number of effective carriers are identified through in vitro screening of the PBAE platform for siLuc delivery to HeLa-Luc cells. Specifically, PA8-C6 and PA8-C8 achieve remarkable gene knockdown efficacies of up to 80% with low cytotoxicity. Certain materials from the PA2 and PA5 series demonstrate potent siRNA delivery capabilities associated with elevated cytotoxicity. The pKa value of PBAE is predominantly determined by the hydrophilic amine side chains rather than the end-capping groups. A pKa range of ≈6.2-6.5 may contribute to the excellent delivery capability for PA8 series carriers. The co-formulation of PBAE carriers with helper lipids leads to the reduced size and surface charges of the polyplex NPs with siRNA, consequently decreasing the cytotoxicity and enhancing siRNA delivery efficacy. These findings hold significant implications for the development of novel degradable polymer carriers for siRNA delivery.

Targeting the phosphatidylglycerol lipid: An amphiphilic dendrimer as a promising antibacterial candidate.

The rapid emergence and spread of multidrug-resistant bacterial pathogens require the development of antibacterial agents that are robustly effective while inducing no toxicity or resistance development. In this context, we designed and synthesized amphiphilic dendrimers as antibacterial candidates. We report the promising potent antibacterial activity shown by the amphiphilic dendrimer AD1b, composed of a long hydrophobic alkyl chain and a tertiary amine-terminated poly(amidoamine) dendron, against a panel of Gram-negative bacteria, including multidrug-resistant Escherichia coli and Acinetobacter baumannii. AD1b exhibited effective activity against drug-resistant bacterial infections in vivo. Mechanistic studies revealed that AD1b targeted the membrane phospholipids phosphatidylglycerol (PG) and cardiolipin (CL), leading to the disruption of the bacterial membrane and proton motive force, metabolic disturbance, leakage of cellular components, and, ultimately, cell death. Together, AD1b that specifically interacts with PG/CL in bacterial membranes supports the use of small amphiphilic dendrimers as a promising strategy to target drug-resistant bacterial pathogens and addresses the global antibiotic crisis.

Probing the Influence of Hydrophobicity of Modified Gold Nanoparticles in Modulating the Lipid Surface Behavior Using Vibrational Sum Frequency Generation Spectroscopy.

A deep understanding of how the surface modifications of nanoparticles impact their interactions with cell membranes is vital for advancing safe and effective biomedical applications. Among the pivotal factors governing these interactions, the hydrophobicity of nanoparticles plays a crucial role, predominantly driven by the hydrophobic interactions with the cell membrane. Herein, we study the influence of the hydrophobic alkyl chain length of thiol-capped gold nanoparticles (GNPs) on lipid surfaces with the help of vibrational sum frequency generation spectroscopy. We have utilized the zwitterionic 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid monolayer as a representative model of cell membranes on the water surface. Our findings revealed that GNPs capped with the thiol ligand having a shorter alkyl chain such as heptanethiol (HT, C7) show minimal changes in the C-H stretching vibrations while interacting with the lipid monolayer. These observations could be attributed to the perturbation of the lipid chain due to hydrophobic-hydrophobic interactions between the alkyl chain of thiol-capped GNPs and the hydrophobic group of the lipid membrane or simply by the adsorption of GNPs at the interface without disrupting the monolayer structure. However, with increasing the chain length of thiol-capped GNPs from decanethiol (DDT, C10) to octadecanethiol (ODT, C18), the extent of spectral change in the C-H stretching vibration is increased. The controlled experiment performed with the deuterated lipids conforms that the changes observed in the C-H stretching vibration after adding HT (C7) GNPs are only because of their presence in the surface without altering the monolayer structure. However, in the case of DT (C10) and DDT (C12) GNPs, the strong hydrophobic interactions between the monolayer and the alkyl chain of the thiol-capped GNPs result in the increased orientational order of the monolayer. Moreover, in the case of ODT (C18) GNPs, the very long alkyl chain induces pronounced perturbations in the monolayer structure with net disordering of the monolayer. These observations are further supported by the spectral changes observed in the O-H vibration of the interfacial water molecules. Our findings reveal the crucial role of the hydrophobic nature of GNPs in influencing the interface. Understanding these effects is crucial for drug delivery applications and improving the stability and effectiveness of lipid-based systems.

Engineering Entomopathogenic Fungi Using Thermal-Responsive Polymer to Boost Their Resilience against Abiotic Stresses.

Entomopathogenic fungi offer an ecologically sustainable and highly effective alternative to chemical pesticides for managing plant pests. However, the efficacy of mycoinsecticides in pest control suffers from environmental abiotic stresses, such as solar UV radiation and temperature fluctuations, which seriously hinder their practical application in the field. Herein, we discovered that the synthetic amphiphilic thermal-responsive polymers are able to significantly enhance the resistance of Metarhizium robertsii conidia against thermal and UV irradiation stresses. The thermosensitive polymers with extremely low cytotoxicity and good biocompatibility can be engineered onto the M. robertsii conidia surface by anchoring hydrophobic alkyl chains. Further investigations revealed that polymer supplementation remarkably augmented the capacity for penetration and the virulence of M. robertsii under heat and UV stresses. Notably, broad-spectrum entomopathogenic fungi can be protected by the polymers. The molecular mechanism was elucidated through exploring RNA sequencing and in vivo/vitro enzyme activity assays. This work provides a novel avenue for fortifying the resilience of entomopathogenic fungi, potentially advancing their practical application as biopesticides.

Hydrophobic modification of biomass chitosan for treatment of oily wastewater and its demulsification mechanism

Traditional demulsifiers are commonly produced using raw materials like ethylene oxide and propylene oxide, which deplete significant petroleum resources and involve hazardous and complex manufacturing processes. In this investigation, a hydrophobically modified chitosan (HMC) was synthesized by grafting dodecyl diethanolamine onto natural chitosan to facilitate the separation of O/W emulsions. Characterization of HMC was conducted using Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance hydrogen spectroscopy (1H NMR) and scanning electron microscopy (SEM). The demulsification efficacy of HMC was assessed through a bottle test in an O/W emulsion containing 0.2 % crude oil. Results showed that at a HMC dosage of 40 mg/L, the light transmission (WT) and oil removal efficiency (WR) of the resulted water phase were 93.4 ± 0.8 % and 99.8 ± 0.1 %, respectively. Furthermore, the competitive adsorption between natural surfactants and HMC at the interface was investigated using interfacial tension (IFT), three-phase contact angle (CA), droplet coalescence time (CTA), and interfacial film substitution. A potential demulsifying mechanism was also proposed, emphasizing HMC’s hydrophilic core and dispersed hydrophobic alkyl chains that enable rapid diffusion to the oil–water interface, replacing interfacial active components to induce demulsification by destabilizing the composite film. The advantages of HMC demulsifier over commercial demulsifiers lie in its superior environmental benefits, diverse range of sources, higher efficiency, and outstanding demulsification performance.

Formation and evolution of nanobubbles in CH4-H2O-Alcohol system: Insight into the effect of alcohol chain length from molecular dynamics simulations

Nanobubbles (NBs) which are gas filled cavities of nanometre dimensions present in liquids attracted increasing attention in the recent years due to their application in various fields such as chemistry, biology, medicine etc. An important aspect of NB research is the study of effect of additives on formation and evolution of these bubbles. The present study examined by applying molecular dynamics simulations, the formation and evolution of methane NBs in the CH4-H2O-Alcohol system, which is known to form during alcohol induced dissociation of CH4 hydrates in the natural gas extraction process. The effect of alcohol type and concentration on NB formation and evolution was examined through simulations of CH4-H2O-CH3OH, CH4-H2O-C2H5OH and CH4-H2O-nC3H7OH systems. The study revealed that increase in both concentration and the alkyl chain length of alcohols promoted NB formation. Alcohol molecules are found to enhance NB nucleation through accumulation near the NB-liquid interface resulting in a decrease in the surface tension (γ) at the interface. These effects become more pronounced as the alkyl chain length increases which explains the enhanced NB formation in systems containing nC3H7OH and C2H5OH compared to those containing CH3OH. The mechanism of formation and evolution of NBs is found to significantly depend on the type of alcohol present. NBs are found to nucleate at multiple locations in the systems containing nC3H7OH and C2H5OH which eventually coalesce to form a single large stable NB. In the presence of NBs which vary significantly in size, bubble growth was also found to occur through Ostwald ripening which involves transfer of CH4 from smaller NB to the larger one. In contrast, in the CH4-H2O-CH3OH system, primarily a single NB nucleated which grew in size through absorption of CH4 molecules dissolved in the liquid, rather than through coalescence or Ostwald ripening. The observed influence of alcohol type on the process of NB evolution is explained by examining the influence of alkyl chain length on γ and diffusivity of CH4 molecules. Due to the role of NBs on methane hydrate regeneration from the hydrate melt, we examined the influence of NB in the CH4-H2O-Alcohol system on the organization of water molecules (HSWs) present in the hydration shell of dissolved CH4. The value of F4 order parameter of HSWs and the number of hydrogen bonded water rings in the hydration shell of CH4 were analysed. The value of F4 order parameter indicate that the hydrophobic alkyl chain of alcohol induced hydrate like arrangement of HSWs, which is more pronounced in the case of alcohol with longer alkyl chain. However, alcohol molecules are also found to dislodge HSWs around CH4 resulting in a decrease in the number of water rings around dissolved CH4 which is not conducive to hydrate formation. These observations are consistent with the reported dual effect of alcohol on hydrate formation with alcohol promoting hydrate formation at low concentrations and inhibiting at high concentrations.

Achieving the hydrophobic alteration by functionalized nano-silica for improving shale hydration inhibition

Shale hydration is the primary cause of wellbore instability during drilling processes. In this study, two non-fluorinated silane-coupling agents, octyltriethoxysilane (OTES) and (3-Aminopropyl) triethoxysilane (APTES), were grafted onto the nano-silica surface to develop a hydrophobic material (SHM). Various performance characterizations, including infrared spectroscopy, thermogravimetric analysis, surface tension, wetting alteration, capillary self-suction height, bentonite expansion, and shale dispersion, were employed to investigate the shale inhibition properties of SHM comprehensively. Experimental results revealed that SHM could significantly improve shale hydration inhibition. For instance, in a 2 % SHM liquids, the shale hot rolling recovery rate increased from 25.39 % to 83.78 %, and the bentonite expansion height decreased from 7.65 mm to 2.80 mm. The inhibition performance was notably superior to potassium chloride (KCl) and polyether amine (PEA). Inhibition mechanisms analysis unveiled that the outstanding inhibitory effect of SHM was achieved through electrostatic adsorption, wettability alteration, and surface tension reduction. Firstly, SHM contained numerous amine groups that could demonstrate strong adsorption on the clay surface through electrostatic and hydrogen bonding interactions. Secondly, with long hydrophobic alkyl chains, it formed a highly hydrophobic film enveloping the shale surface, effectively preventing water from invading. Thirdly, it reduced liquid surface tension, further minimizing the water infiltration. As a result, the use of SHM significantly enhanced shale hydration inhibition during the shale drilling process.

Photophysical Response of Propranolol in Biomimetic Micellar Media of Alkyltrimethylammonium Bromide Surfactants: Effect of pH and Alkyl Chain Length.

The photophysical behavior of a β-blocker drug propranolol (PPL) in micellar environments, formed by alkyltrimethylammonium bromide surfactants viz.; Cetyltrimethylammonium bromide (CTAB), Tetradecyltrimethylammonium bromide (TTAB), and Dodecyltrimethylammonium bromide (DTAB), has been investigated through fluorescence and UV-visible spectroscopic techniques at pH levels of 3.5, 7.4, and 10.4. The impact of pH on the critical micelle concentration (cmc) and micropolarity of micelles were assessed using pyrene as a photophysical probe. The cmc values were found to be lower at pH 10.4 compared to pH 7.4 and pH 3.5. Fluorescence emission intensities of PPL at 323nm, 338nm, and 352nm were significantly influenced by pH, hydrophobic alkyl chain length of surfactants, and their concentrations. Quenching experiments with Cetylpyridinium chloride (CpCl) indicated the localization of charged and uncharged forms of PPL within micelles, with quenching constant (Ksv) values dependent on alkyl chain length and pH. At pH < pKa, PPL is positioned near the Stern layer, whereas at pH 10.4, its naphthalene moiety resides near the hydrophobic micellar core. UV spectroscopy showed that the charged form of PPL interacted with micelles only above cmc, while the neutral form interacted even below the cmc. Density Functional Theory (DFT) reveals the HOMO of the surfactants to be localized on the hydrocarbon chains, and the LUMO localized around the quaternary ammonium unit. Upon complexation with PPL, both HOMO and LUMO shifted to the drug, thereby decreasing energy levels. The findings are explained based on weak noncovalent interactions, further supported and analyzed through Reduced Density Gradient (RDG) and Noncovalent Interaction (NCI) methods, confirming synergistic non-covalent interactions in surfactant-PPL complexes.

Antiscaling Pickering Emulsions Enabled by Amphiphilic Hairy Cellulose Nanocrystals.

Nucleation and growth of sparingly soluble salts, referred to as scaling, has posed substantial challenges in industrial processes that deal with multiphase flows, including enhanced oil recovery (EOR). During crude oil extraction/recovery, seawater is injected into oil reservoirs and yields water-in-oil (W/O) emulsions that may undergo calcium carbonate (CaCO3) scaling. Common antiscaling macromolecules and nanoparticles have adverse environmental impacts and/or are limited to functioning only in single-phase aqueous media. Here, we develop a novel antiscaling cellulose-based nanoparticle that enables scale-resistant Pickering emulsions. Cellulose fibrils are rationally nanoengineered to yield amphiphilic hairy cellulose nanocrystals (AmHCNC), bearing hydrophilic dicarboxylate groups and hydrophobic alkyl chains on disordered cellulose chains (hairs) protruding from nanocrystal ends. The unique chemical and structural properties of AmHCNC render them the first dual functional antiscaling and emulsion stabilizing nanoparticle. AmHCNC stabilize W/O Pickering emulsions at a concentration of 1.00 wt % for 1 week while inhibiting CaCO3 scale formation up to 70% by mass at a supersaturation degree of ∼101 compared with the synthetic surfactant Span 80. To the best of our knowledge, this study presents the first biopolymer-based solution for the long-lasting scaling challenge in multiphase media, which may set the stage for developing sustainable scale-resistant multiphase flows in a broad spectrum of industrial sectors.

Amphipathic Surfactant on Reconstructed Bismuth Enables Industrial-Level Electroreduction of CO2 to Formate.

Developing efficient electrocatalysts for selective formate production via the electrochemical CO2 reduction reaction (CO2RR) is challenged by high overpotential, a narrow potential window of high Faradaic efficiency (FEformate), and limited current density (Jformate). Herein, we report a hierarchical BiOBr (CT/h-BiOBr) with surface-anchored cetyltrimethylammonium bromide (CTAB) for formate-selective large-scale CO2RR electrocatalysis. CT/h-BiOBr achieves over 90% FEformate across a wide potential range (-0.5 to -1.1 V) and an industrial-level Jformate surpassing 100 mA·cm-2 at -0.7 V. In situ investigations uncover the reconstructed Bi(110) surface as the active phase, with CTAB playing a dual role: its hydrophobic alkyl chains create a CO2-enriching microenvironment, while its polar head groups fine-tune the electronic structure, fostering a highly active phase. This work provides valuable insights into the role of surfactants in electrocatalysis and guides the design of electrocatalysts for the large-scale CO2RR.

Organosilane-assisted synthesis of EU-1 nanozeolite aggregates with improved activity in catalytic cracking of n-hexane

One-dimensional microporous zeolite, EU-1, exhibits more favorable selectivity of propylene in cracking of petroleum components. However, it faced the problem of low catalytic activity for the poor utilization of active sites. In this work, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC) was used to functionalize protozeolitic units and inhibit the excessive growth of crystals by the long hydrophobic alkyl chain. The introduction of TPOAC decreased the crystal sizes into nanoscale, enhanced the mesoporous volume of EU-1 zeolite, and exposed more external acid sites. Moreover, TPOAC could interact with Al species, and in this case, fewer Al atoms were incorporated into the zeolite framework, reducing the acid strength and amount. Intelligent gravitation analyzer test indicated that the zeolite prepared with the presence of 0.30 g TPOAC exhibited the largest accessible volumes in n-hexane adsorption, and the highest accessibility of acid sites, which synergistically promoted cracking of n-hexane for the production of light olefins.

The study of antibacterial activity of cationic poly(β-amino ester) regulating by amphiphilic balance

It is well known that cationic polymers have excellent antimicrobial capacity accompanied with high biotoxicity, to reduce biotoxicity needs to decrease the number of cationic groups on polymers, which will influence antimicrobial activity. It is necessary to design a cationic polymer mimic natural antimicrobial peptide with excellent antibacterial activity and low toxicity to solve the above dilemma. Here, we designed and prepared a series of cationic poly(β-amino ester)s (PBAEs) with different cationic contents, and introducing hydrophobic alkyl chain to adjust the balance between antimicrobial activity and biotoxicity to obtain an ideal antimicrobial polymer. The optimum one of synthesized PBAE (hydrophilic cationic monomer :hydrophobic monomer = 5:5) was screened by testing cytotoxicity and minimum inhibitory concentration (MIC), which can effectively kill S. aureus and E. coli with PBAE concentration of 15 μg/mL by a spread plate bacteriostatic method and dead and alive staining test. The way of PBAE killing bacterial was destroying the membrane like natural antimicrobial peptide observed by scanning electron microscopy (SEM). In addition, PBAE did not exhibit hemolysis and cytotoxicity. In particular, from the result of animal tests, the PBAE was able to promote healing of infected wounds from removing mature S. aureus and E. coli on the surface of infected wound. As a result, our work offers a viable approach for designing antimicrobial materials, highlighting the significant potential of PBAE polymers in the field of biomedical materials.

Antibacterial Hydrogel Adhesives Based on Bifunctional Telechelic Dendritic-Linear-Dendritic Block Copolymers.

Antibiotic-resistant pathogens have been declared by the WHO as one of the major public health threats facing humanity. For that reason, there is an urgent need for materials with inherent antibacterial activity able to replace the use of antibiotics, and in this context, hydrogels have emerged as a promising strategy. Herein, we introduce the next generation of cationic hydrogels with antibacterial activity and high versatility that can be cured on demand in less than 20 s using thiol-ene click chemistry (TEC) in aqueous conditions. The approach capitalizes on a two-component system: (i) telechelic polyester-based dendritic-linear-dendritic (DLDs) block copolymers of different generations heterofunctionalized with allyl and ammonium groups, as well as (ii) polyethylene glycol (PEG) cross-linkers functionalized with thiol groups. These hydrogels resulted in highly tunable materials where the antibacterial performance can be adjusted by modifying the cross-linking density. Off-stoichiometric hydrogels showed narrow antibacterial activity directed toward Gram-negative bacteria. The presence of pending allyls opens up many possibilities for functionalization with biologically interesting molecules. As a proof-of-concept, hydrophilic cysteamine hydrochloride as well as N-hexyl-4-mercaptobutanamide, as an example of a thiol with a hydrophobic alkyl chain, generated three-component networks. In the case of cysteamine derivatives, a broader antibacterial activity was noted than the two-component networks, inhibiting the growth of Gram-positive bacteria. Additionally, these systems presented high versatility, with storage modulus values ranging from 270 to 7024 Pa and different stability profiles ranging from 1 to 56 days in swelling experiments. Good biocompatibility toward skin cells as well as strong adhesion to multiple surfaces place these hydrogels as interesting alternatives to conventional antibiotics.

Self-assembling dendrimer nanosystems for specific fluorine magnetic resonance imaging and effective theranostic treatment of tumors

Fluorine magnetic resonance imaging (19F-MRI) is particularly promising for biomedical applications owing to the absence of fluorine in most biological systems. However, its use has been limited by the lack of safe and water-soluble imaging agents with high fluorine contents and suitable relaxation properties. We report innovative 19F-MRI agents based on supramolecular dendrimers self-assembled by an amphiphilic dendrimer composed of a hydrophobic alkyl chain and a hydrophilic dendron. Specifically, this amphiphilic dendrimer bears multiple negatively charged terminals with high fluorine content, which effectively prevented intra- and intermolecular aggregation of fluorinated entities via electrostatic repulsion. This permitted high fluorine nuclei mobility alongside good water solubility with favorable relaxation properties for use in 19F-MRI. Importantly, the self-assembling 19F-MRI agent was able to encapsulate the near-infrared fluorescence (NIRF) agent DiR and the anticancer drug paclitaxel for multimodal 19F-MRI and NIRF imaging of and theranostics for pancreatic cancer, a deadly disease for which there remains no adequate early detection method or efficacious treatment. The 19F-MRI and multimodal 19F-MRI and NIRF imaging studies on human pancreatic cancer xenografts in mice confirmed the capability of both imaging modalities to specifically image the tumors and demonstrated the efficacy of the theranostic agent in cancer treatment, largely outperforming the clinical anticancer drug paclitaxel. Consequently, these dendrimer nanosystems constitute promising 19F-MRI agents for effective cancer management. This study offers a broad avenue to the construction of 19F-MRI agents and theranostics, exploiting self-assembling supramolecular dendrimer chemistry.

Metabolism of alcohol ethoxylates (AEs) in rat, hamster, and human hepatocytes and liver S9: a pilot study for metabolic stability, metabolic pathway, and metabolites identification in vitro and in silico

Alcohol ethoxylates (AEs) are a well-known class of non-ionic surfactants widely used by the personal care market. The aim of this study was to evaluate and characterize the in vitro metabolism of AEs and identify metabolites. Five selected individual homologue AEs (C8EO4, C10EO5, C12EO4, C16EO8, and C18EO3) were incubated using human, rat, and hamster liver S9 fraction and cryopreserved hepatocytes. LC–MS was used to identify metabolites following the incubation of AEs by liver S9 and hepatocytes of all three species. All AEs were metabolized in these systems with a half-life ranging from 2 to 139 min. In general, incubation of AE with human liver S9 showed a shorter half-life compared to rat liver S9. While rat hepatocytes metabolized AEs faster than human hepatocytes. Both hydrophobic alkyl chain and hydrophilic EO head group groups of AEs were found to be target sites of metabolism. Metabolites were identified that show primary hydroxylation and dehydrogenation, followed by O-dealkylation (shortening of EO head groups) and glucuronidation. Additionally, the detection of whole EO groups indicates the cleavage of the ether bond between the alkyl chain and the EO groups as a minor metabolic pathway in the current testing system. Furthermore, no difference in metabolic patterns of each individual homologue AE investigated was observed, regardless of alkyl chain length or the number of EO groups. Moreover, there is an excellent agreement between the in vitro experimental data and the metabolite profile simulations using in silico approaches (OECD QSAR Toolbox). Altogether, these data indicate fast metabolism of all AEs with a qualitatively similar metabolic pathway with some quantitative differences observed in the metabolite profiles. These metabolic studies using different species can provide important reference values for further safety evaluation.

CO2-responsive polymer promoted by polyether to efficient viscosity increase for CO2 plugging

A novel series of CO2-responsive polymers with unique hydrophobic structures were developed, capable of efficiently increasing viscosity in response to CO2 at low concentrations. These polymers, namely PAD-H, were synthesized by copolymerizing acrylamide, 2-(dimethylamino)ethyl methacrylate, and octadecyl polyoxyethylene ether methacrylate. In parallel, two comparative polymer sets were crafted, lacking the long polyether chains in their hydrophobic structures. DMAEMA imparts CO2-responsiveness through its tertiary amine groups, while the hydrophobic monomer contributes an alkyl structure with polyether long chains. These hydrophilic polyether long chains provide enhanced mobility to the hydrophobic alkyl chains, enabling lower concentration molecular hydrophobic association post CO2 exposure, thus leading to an increase in viscosity. This research delved into the mechanism of CO2-responsive viscosity increase, examining the impact of the polymer's intrinsic structure and external factors on its responsive behavior. Additionally, the polymer was applied in CO2 flooding, a crucial technique in carbon capture, utilization, and storage (CCUS). Simulated reservoir conditions were used to conduct in-situ CO2-responsive viscosity increase tests and CO2 gas channeling plugging experiments, substantially enhancing plugging efficiency. This advancement offers practical materials for addressing gas channeling in CO2 flooding and augments the technical methodologies for carbon utilization and storage within the CCUS framework.

Structure Optimization and Passivation Strategy Toward Efficient Integrated Perovskite/Pseudo‐Planar Heterojunction Solar Cells

AbstractBroadening near‐infrared (NIR) spectral response by virtue of organic bulk heterojunction (BHJ) is intensively explored to enhance power conversion efficiency (PCE) of perovskite solar cells (PSCs). However, the complex photovoltaic morphology and undesirable conductivity in BHJ structure can lead to the severe loss of photovoltaic performance, which are still urgent challenges for the commercialization of integrated PSCs (IPSCs). Recently, the gradual development of pseudo‐planar heterojunction (PPHJ) structure with excellent vertical phase separation and improved charge transfer can hopefully provide more opportunities for IPSCs. Herein, an optimization strategy is reported employing PPHJ structure with hydrophobic long alkyl chains as the NIR light‐absorbing layer in the devices, with which the light response of the IPSCs is extended to 920 nm. Owing to the lone electron pairs in the sulfur atoms, D18‐Cl has functioned as an effective additive that can effectively modulate the growth of the perovskite and passivate the defects. As a result, the optimized device has achieved an impressive PCE of 23.25%, while the short‐circuit current is enhanced from 22.93 to 25.14 mA cm−2. The long‐term and humidity stability of integrated perovskite/PPHJ solar cells are significantly elevated compared with IPSCs based on BHJ.

Incorporating porous carbon materials into ionic liquid for high efficiency extraction of polycyclic aromatic hydrocarbons

Ionic liquid is an ideal candidate in the extraction of aromatic compounds. The design and construction of ionic liquids with high extraction efficiency and selectivity towards to the specific aromatics remain crucial question. In this paper, with the aid of orthogonal array experiment, the imidazolium-based ionic liquids with long alkyl chain on the cations were determined to possess high aromatics extraction efficiency. Furthermore, the Lewis acid anion was introduced into the ionic liquid to form 1-dodecyl-3-methylimidazolium ferric chloride ([C12mim][FeCl4]) and performed 62 % and 100 % extractant efficiency of naphthalene (NAP) and anthracene (ANT), respectively. Then the porous carbon materials (P1-1000) derived from hyper-crosslinked porous polymers (HCP) which possessed high BET surface area (1186 m2/g) was dispersed in [C12mim][FeCl4] to form porous ionic liquid. The single extraction efficiency of NAP improved from 62 % to 77 %. The great single extraction efficiency was attributed to the high porosity, additional adsorption sites provided by the Lewis acid anions and the hydrophobic long alkyl chain on the cations. After three times extraction, the concentration of NAP dropped down to 0. The porous ionic liquids also showed good recycle performance. The construction of porous ionic liquids provided an efficient approach for extraction of polycyclic aromatic hydrocarbons from aliphatic hydrocarbon.