Monomethyl Ether Research Articles

STAT3-specific nanocarrier for shRNA/drug dual delivery and tumor synergistic therapy

Non-small cell lung cancer (NSCLC) is a major disease with high incidence, low survival rate and prone to develop drug resistance to chemotherapy. The mechanism of secondary drug resistance in NSCLC chemotherapy is very complex, and studies have shown that the abnormal activation of STAT3 (Signal Transducer and Activator of Transcription 3) plays an important role in it. In this study, the pGPU6/GFP/Neo STAT3-shRNA recombinant plasmid was constructed with STAT3 as the precise target. By modifying hydrophilic and hydrophobic blocks onto chitosan, a multifunctional vitamin E succinate-chitosan-polyethylene glycol monomethyl ether histidine (VES-CTS-mPEG-His) micelles were synthesized. The micelles could encapsulate hydrophobic drug doxorubicin through self-assembly, and load the recombinant pGPU6/GFP/Neo STAT3-shRNA (pDNA) through positive and negative charges to form dual-loaded nanoparticles DOX/VCPH/pDNA. The co-delivery and synergistic effect of DOX and pDNA could up-regulate the expression of PTEN (Phosphatase and Tensin Homolog), down-regulate the expression of CD31, and induce apoptosis of tumor cells. The results of precision targeted therapy showed that DOX/VCPH/pDNA could significantly down-regulate the expression level of STAT3 protein, further enhancing the efficacy of chemotherapy. Through this study, precision personalized treatment of NSCLC could be effectively achieved, reversing its resistance to chemotherapy drugs, and providing new strategies for the treatment of drug-resistant NSCLC.

Unveiling the Failure Mechanism of Zn Anodes in Zinc Trifluorosulfonate Electrolyte: The Role of Micelle-like Structures.

Zinc trifluorosulfonate [Zn(OTf)2] is considered as the most suitable zinc salt for aqueous Zn-ion batteries (AZIBs) but cannot support the long-term cycling of the Zn anode. Here, we reveal the micelle-like structure of the Zn(OTf)2 electrolyte and reunderstand the failing mechanism of the Zn anode. Since the solvated Zn2+ possesses a positive charge, it can spontaneously attract OTf- with the hydrophilic group of -SO3 and the hydrophobic group of -CF3 via electrostatic interaction and form a "micelle-like" structure, which is responsible for the poor desolvation kinetics and dendrite growth. To address these issues, an antimicelle-like structure is designed by using ethylene glycol monomethyl ether (EGME) as a cosolvent for highly reversible AZIBs. The modified electrolyte shows lower dissociation ability to Zn(OTf)2 and higher coordination tendency with Zn2+ compared to the Zn(OTf)2 electrolyte, resulting in the unique solvation structure of Zn2+(H2O)1.2(OTf-)2(EGME)2.8, which significantly reduces the charge of micelle, damages the micelle-like structure, and boosts the desolvation kinetics. Moreover, the reduction of EGME and OTf- can form a robust dual-layered SEI with high Zn2+ ion conductivity. Consequently, the Zn/Cu asymmetric coin cell using ZT-EGME can work at a high rate and a capacity of 50 mA cm-2 and 5 mA h cm-2 for more than 120 cycles, while its counterparts using ZT can barely work. Moreover, a 505.1 mA h pouch cell with practical parameters including a lean electrolyte supply of 15 mL A h-1 and an N/P ratio of ∼3.5 can work for 50 cycles.

Glycol Monomethyl Ether-Substituted Carbazolyl Hole-Transporting Material for Stable Inverted Perovskite Solar Cells with Efficiency of 25.52 .

Organic self-assembled molecules (OSAMs) based hole-transporting materials play a pivotal role in achieving highly efficient and stable inverted perovskite solar cells (IPSCs). However, the reported carbazol-based OSAMs have serious drawbacks, such as poor wettability for perovskite solution spreading due to the nonpolar surface, worse matched energy arrangement with perovskite, and limited molecular species, which greatly limit the device performance. To address above problems, a novel OSAM [4-(3,6-glycol monomethyl ether-9H-carbazol-9-yl) butyl]phosphonic acid (GM-4PACz) was synthesized as hole-transporting material by introducing glycol monomethyl ether (GM) side chains at carbazolyl unit. GM groups enhance the surface energy of Indium Tin Oxide (ITO)/SAM substrate to facilitate the nucleation and growth of up perovskite film, suppress cation defects, release the residual stress at SAM/perovskite interface, and evaluate energy level for matching with perovskite. Consequently, the GM-4PACz based IPSC achieves a champion PCE of 25.52 %, a respectable open-circuit voltage (VOC) of 1.21 V, a high stability, possessing 93.29 % and 91.75 % of their initial efficiency after aging in air for 2000 h or tracking at maximum power point for 1000 h, respectively.

Glycol Monomethyl Ether‐Substituted Carbazolyl Hole‐Transporting Material for Stable Inverted Perovskite Solar Cells with Efficiency of 25.52 %

AbstractOrganic self‐assembled molecules (OSAMs) based hole‐transporting materials play a pivotal role in achieving highly efficient and stable inverted perovskite solar cells (IPSCs). However, the reported carbazol‐based OSAMs have serious drawbacks, such as poor wettability for perovskite solution spreading due to the nonpolar surface, worse matched energy arrangement with perovskite, and limited molecular species, which greatly limit the device performance. To address above problems, a novel OSAM [4‐(3,6‐glycol monomethyl ether‐9H‐carbazol‐9‐yl) butyl]phosphonic acid (GM‐4PACz) was synthesized as hole‐transporting material by introducing glycol monomethyl ether (GM) side chains at carbazolyl unit. GM groups enhance the surface energy of Indium Tin Oxide (ITO)/SAM substrate to facilitate the nucleation and growth of up perovskite film, suppress cation defects, release the residual stress at SAM/perovskite interface, and evaluate energy level for matching with perovskite. Consequently, the GM‐4PACz based IPSC achieves a champion PCE of 25.52 %, a respectable open‐circuit voltage (VOC) of 1.21 V, a high stability, possessing 93.29 % and 91.75 % of their initial efficiency after aging in air for 2000 h or tracking at maximum power point for 1000 h, respectively.

Deciphering the interactions between altertoxins and glutenin based on molecular dynamic simulation: inspiration from detection.

Mycotoxin contamination of food has been gaining increasing attention. Hidden mycotoxins that interact with biological macromolecules in food could make the detection of mycotoxins less accurate, potentially leading to the underestimation of the total exposure risk. Interactions of the mycotoxins alternariol (AOH) and alternariol monomethyl ether (AME) with high-molecular glutenin were explored in this study. The recovery rates of AOH and AME (1, 2, and 10 μg kg-1) in three types of grains (rice, corn, and wheat) were relatively low. Molecular dynamics (MD) simulations indicated that AOH and AME bound to glutenin spontaneously. Hydrogen bonds and π-π stacking were the primary interaction forces at the binding sites. Alternariol with one additional hydroxyl group exhibited stronger binding affinity to glutenin than AME when analyzing average local ionization energy. The average interaction energy between AOH and glutenin was -80.68 KJ mol-1, whereas that of AME was -67.11 KJ mol-1. This study revealed the mechanisms of the interactions between AOH (or AME) and high-molecular glutenin using MD and molecular docking. This could be useful in the development of effective methods to detect pollution levels. These results could also play an important role in the evaluation of the toxicological properties of bound altertoxins. © 2024 Society of Chemical Industry.

Electrospinning and Partial Etching Behaviors of Core-Shell Nanofibers Directly Electrospun on Mesh Substrates for Application in a Cover-Free Compact Air Filter.

The exposure of workers to propylene glycol monomethyl ether acetate (PGMEA) in manufacturing environments can result in potential health risks. Therefore, systems for PGMEA removal are required for indoor air quality control. In this study, core-shell zeolite socony mobil-5 (ZSM-5)/polyvinylpyrrolidone-polyvinylidene fluoride nanofibers were directly electrospun and partially wet-etched on a mesh substrate to develop a cover-free compact PGMEA air filter. The electrospinning behaviors of the core-shell nanofibers were investigated to optimize the electrospinning time and humidity and to enable the manufacture of thin and light air-filter layers. The partial wet etching of the nanofibers was undertaken using different etching solvents and times to ensure the exposure of the active sites of ZSM-5. The performances of the ZSM-5/PVDF nanofiber air filters were assessed by measuring five consecutive PGMEA adsorption-desorption cycles at different desorption temperatures. The synthesized material remained stable upon repeated adsorption-desorption cycles and could be regenerated at a low desorption temperature (80 °C), demonstrating a consistent adsorption performance upon prolonged adsorption-desorption cycling and low energy consumption during regeneration. The results of this study provide new insights into the design of industrial air filters using functional ceramic/polymer nanofibers and the application of these filters.

Equilibrium solubility and mathematical modelling of glibenclamide in cosolvent mixtures of glycols and alcohols

ABSTRACT Glibenclamide (GBN) is a commonly used oral medication for treating type-II diabetes that acts by reducing high blood sugar levels. The effectiveness of GBN depends on the quality of the product. The quality is influenced by the solubility properties of a drug. This study aimed to measure the solubility of GBN in various solvent mixtures including some glycols and alcohols. The solubility was determined using a shake-flask method at 298.2 K under atmospheric pressure. The results showed that GBN had the highest solubility in ethylene glycol monomethyl ether and alcohol mixtures compared to the other tested glycols.

Copper-Free Synthesis of Cationic Glycidyl Triazolyl Polymers.

Copper-free synthesis of cationic glycidyl triazolyl polymers (GTPs) is achieved through a thermal azide-alkyne cycloaddition reaction between glycidyl azide polymer and propiolic acid, followed by decarboxylation and quaternization of the triazole unit. For synthesizing nonfunctionalized GTP (GTP-H), a microwave-assisted method enhances the decarboxylation reaction of carboxy-functionalized GTP (GTP-COOH). Three variants of cationic GTPs with different N-substituents [N-ethyl, N-butyl, and N-tri(ethylene glycol) monomethyl ether (EG3)] are synthesized. The molecular weight of GTP-H is determined via size exclusion chromatography. Thermal properties of all GTPs are characterized using differential scanning calorimetry and thermogravimetric analysis. The ionic conductivities of these cationic GTPs are assessed by impedance measurements. The conducting ion concentration and mobility are calculated based on the electrode polarization model. Among three cationic GTPs, the GTP with the N-EG3 substituent exhibits the highest ionic conductivity, reaching 6.8 × 10-6 S cm-1 at 25°C under dry conditions. When compared to previously reported reference polymers, the reduction of steric crowding around the triazolium unit is considered to be a key factor in enhancing ionic conductivity.

La:ZnO nanoparticles: an investigation on structural, optical, and microwave properties

This paper presents the utilization of ethylene glycol monomethyl ether (EGME) during the synthesis of ZnO and La:ZnO with two tasks as a solvent and a fuel source within the gel combustion technique. The use of EGME for this purpose provides one-step production of the nanoparticles (NPs) and saves a considerable amount of time. The detailed characterization of the nanoparticles was carried out by X-ray diffractometer (XRD), scanning electron microscope (SEM), particle size analyzer, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Vector Network Analyzer (VNA) measurements, respectively. The NPs exhibited a hexagonal wurtzite structure with good crystallinity and a porous spongy morphology. The photoluminescence emission maxima of the synthesized NPs appeared at 500, 560, and 676 nm, upon excitation by the 372 nm of excitation. La:ZnO NPs showed significantly better photoluminescent characteristics than La-free ZnO forms. When excited at the same wavelength, La-free ZnO, 3%, and 7% La:ZnO exhibited 92, 45, and 35 μs average decay times, respectively. Finally, the microwave properties of the relative complex permittivity and permeability characteristics were also investigated and discussed in detail, which were derived from the scattering parameters of S11 and S21 in the X band regime.

Investigation of the effect of ether oxygenated additives on diesel engine performance, combustion, and exhaust emissions - An experimental approach

Conventional energy sources, including diesel and petrol, are decreasing day by day, while their reserves are limited. However, it is difficult to find alternative fuels to replace them. Hence, to fulfill the growing energy demand and reduce environmental emissions, it is vital to find a wide variety of oxygenated compounds to conventional diesel fuels that show low emission potential from transport engines. In this research, we investigated diesel engine performance, combustion, and exhaust emissions with the addition of 10 %, 15 %, 25 %, and 30 % of three different oxygenated blends, including Diethylene Glycol Dimethyl ether (DGM), Di-n-Butyl Ether (DBE), and Tripropylene-Glycol Monomethyl ether (TPGM). This paper presents the brake-specific fuel consumption (BSFC), Brake Thermal Efficiency (BTE), Brake Mean Effective Pressure (BMEP), and Brake Specific Energy Consumption (BSEC) for these fuel blends. The generated emissions of carbon dioxide (CO2), Carbon Monoxide (CO), and nitrogen oxide (NO) were quantified for four different engine speeds of 1500, 1800, 2000, and 2400 rpm for neat (100 %) oxygenated blends. This research also shows the in-cylinder pressure and heat release rate (HRR) of these three oxygenated blends. The outcome of this paper will help future researchers to develop automobiles and vehicles for oxygenated blends with conventional fuels.

Novel side-reactor dividing wall column and reactive distillation process for enhanced electronic-grade propylene glycol monomethyl ether acetate production

The semiconductor industry is experiencing rapid growth and has become one of the largest sectors in the world. Propylene glycol monomethyl ether acetate (PGMEA) is prized for its exceptional properties and its ability to meet the stringent requirements as a solvent for electronic processing. This work aims to enhance the production of electronic-grade PGMEA through a practical and advanced intensified configuration. First, the kinetic reactor for propylene glycol monomethyl ether (PGME) synthesis has been modeled and pinpointed optimal operating conditions through sensitivity analysis. Subsequently, several process alternatives incorporating intensified techniques, such as the dividing wall column (DWC), pressure swing distillation (PSD), reactive DWC (RDWC), and side-reactor DWC (SR-DWC), have been investigated. These processes have been systematically designed and optimized through a sequential design procedure. Response surface methodology, a practical optimization method, has been employed to optimize the complex column's structure with the help of Aspen Plus and Minitab. Energy requirements and costs of all process alternatives were evaluated for a fair comparison. The SR-DWC-RD process has emerged as the most promising option, as it can save up to 11.5 % in energy requirements and 19.9 % in total annual costs. This practical design, complete with detailed optimal design parameters, presents significant opportunities for improving industrial PGMEA production.

A Versatile Cryomicroneedle Patch for Traceable Photodynamic Therapy.

Photodynamic therapy (PDT) continues to encounter multifarious hurdles, stemming from the ineffectual preservation and delivery system of photosensitizers, the dearth of imaging navigation, and the antioxidant/hypoxic tumor microenvironment. Herein, a versatile cryomicroneedle patch (denoted as CMN-CCPH) is developed for traceable PDT. The therapeutic efficacy is further amplified by catalase (CAT)-induced oxygen (O2) generation and Cu2+-mediated glutathione (GSH) depletion. The CMN-CCPH is composed of cryomicroneedle (CMN) as the vehicle and CAT-biomineralized copper phosphate nanoflowers (CCP NFs) loaded with hematoporphyrin monomethyl ether (HMME) as the payload. Importantly, the bioactive function of HMME and CAT can be optimally maintained under the protection of CCPH and CMN for a duration surpassing 60 days, leading to bolstered bioavailability and notable enhancements in PDT efficacy. The in vivo visualization of HMME and oxyhemoglobin saturation (sO2) monitored by fluorescence (FL)/photoacoustic (PA) duplex real-time imaging unveils the noteworthy implications of CMN-delivered CCPH for intratumoral enrichment of HMME and O2 with reduced systemic toxicity. This versatile CMN patch demonstrates distinct effectiveness in neoplasm elimination, underscoring its promising clinical prospects.

Development and validation of stable isotope dilution LC–MS/MS method for simultaneous quantification of four Alternaria toxins in 15 food commodities

Alternaria toxins (ATs) are produced from Alternaria species that result in crop losses and harmful impacts on human health. A stable isotope dilution LC–MS/MS method was established to quantify four ATs in 15 food commodities: alternariol (AOH), alternariol monomethyl ether (AME), tentoxin (TEN), and tenuazonic acid (TeA). Based on systematically optimization of detection conditions and pre-processing steps, the limits of detection and limits of quantification of the four ATs ranged from 0.1 to 10 μg/kg and 0.2 to 30 μg/kg, respectively. The results showed that the recoveries of the four ATs were 72.0%–119.1%. The intra-precision and inter-precision ranged from 0.7% to 11.1% and 1.1% to 13.1%, respectively. The method was successfully applied to the determination of four ATs in 35 food samples, suggesting that this method could provide meaningful occurrence data to support the assessment of emerging ATs in food commodities.

Isolation of stilbenoids from fresh knotwood of Scots pine using a high yield method

Abstract Scots pine knotwood contains valuable amount of stilbenoids such as pinosylvin (Ps) and pinosylvin monomethyl ether (PsMME). The stilbenoids have numerous biological activities. Traditional methods of extracting stilbenoids often yield low quantities and involve complex processes. In the present study, a simple and high-yield method was proposed for the extraction of stilbenoids from fresh Scots pine knotwood using ethanol taking a total of three days. In addition, the impact of drying process, extraction time, extraction solvents (acetone and ethanol) and storage time were evaluated on the yield of the stilbenoids. The increased yield and improved extraction efficiency make this method a promising advancement for promoting the utilization of stilbenoids for their valuable bioactive properties.

Carbon dots loaded polycarbonate thermosensitive hydrogel: An innovative strategy for promoting infected wound healing

The healing process of bacterial infection wounds is a complex and chronic issue that poses a significant threat to human health. Thermosensitive antibacterial hydrogels, which transition from sol to gel at body temperature, have emerged as a promising option for wound dressing to accelerate healing and prevent infections. In this paper, we present a thermosensitive hydrogel (PTPH) made from (Polyethylene glycol monomethyl ether)-b-(polytrimethylene carbonate)-b-(polyethylene glycol monomethyl ether) (mPEG12-PTMCn-mPEG12, PTP) triblock copolymers, showing gel transition properties at around 34 °C. Additionally, (spermidine)-(ortho-phenylenediamine) carbon dots (SCDs) were enclosed within PTPH (PTPH-SCDs) to provide antibacterial activity against Escherichia coli and Staphylococcus aureus. In vitro experiments demonstrated that PTPH-SCDs have good skin adhesion, excellent biocompatibility, and exceptional antimicrobial efficacy. In vivo studies on a Sprague-Dawley rat model infected with Staphylococcus aureus showed that PTPH-SCDs dressings enhance the healing of infected wounds by inhibiting bacterial proliferation, promoting collagen deposition, and stimulating angiogenesis. This research presents a novel approach for developing multifunctional wound dressing by incorporating carbon dots into aliphatic polycarbonate based temperature-responsive hydrogels for the treatment of infected wounds.

UV/esterase dual responsive nanosystems based on protoporphyrin IX-polyethylene glycol monomethyl ether for enhanced photodynamic bactericidal and herbicidal effects

Photoactivated pesticides with high activity, environmental friendliness, and no drug resistance represent the direction of pesticide development. However, poor photostability and lack of targeting ability greatly restrict their practical application. Herein, a novel amphiphilic photoactivated polymeric propesticide was synthesized by conjugation of mPEG with the photo/enzyme-labile o-nitrobenzyl ester group followed by grafting protoporphyrin IX (PpIX), which could self-assemble into photo/esterase responsive polymer micelles in aqueous solutions for a controlled release of PpIX. The fluorescence quenching caused by the aggregation of PpIX into hydrophobic core could enhance its photostability. UV/esterase stimulation could trigger the release of PpIX and restore its photodynamic activity. Compared to a single stimulus, dual stimulation could trigger more PpIX release and resulting in higher photodynamic activity and antibacterial effect. In addition, light exposure also showed little influence on the photodynamic activity and antibacterial effect of the system due to enhanced photostability. Compared with PpIX, the nanosystem exhibited higher wettability and retention ability on plant leaves and could resist rainwater washout. Weed control experiment also demonstrated that the system’s control effect on barnyard grass. Therefore, this study provides new ideas for promoting the application of photoactivated pesticides in the field of plant protection.

Post-processing of a 3D-printed denture base polymer: Impact of a centrifugation method on the surface characteristics, flexural properties, and cytotoxicity

ObjectivesTo investigate the impact of a centrifugation method on the surface characteristics, flexural properties, and cytotoxicity of an additively manufactured denture base polymer. MethodsThe tested specimens were prepared by digital light processing (DLP). A centrifugation method (CENT) was used to remove the residual uncured resin. In addition, the specimens were post-processed with different post-rinsing solutions: isopropanol (IPA), ethanol (EtOH), and tripropylene glycol monomethyl ether (TPM), respectively. A commercial heat-polymerized polymethyl methacrylate was used as a reference (REF). First, the values of surface topography, arithmetical mean height (Sa), and root mean square height (Sq) were measured. Next, flexural strength (FS) and modulus were evaluated. Finally, cytotoxicity was assessed using an extract test. The data were statistically analyzed using a one-way analysis of variance, followed by Tukey's multiple comparison test for post-hoc analysis. ResultsThe Sa value in the CENT group was lower than in the IPA, EtOH, TPM, and REF groups (p < 0.001). Moreover, the CENT group had lower Sq values than other groups (p < 0.001). The centrifugation method showed a higher FS value (80.92 ± 8.65 MPa) than the EtOH (61.71 ± 12.25 MPa, p < 0.001) and TPM (67.01 ± 9.751 MPa, p = 0.027), while affecting IPA (72.26 ± 8.80 MPa, p = 0.268) and REF (71.39 ± 10.44 MPa, p = 0.231). Also, the centrifugation method showed no evident cytotoxic effects. ConclusionsThe surfaces treated with a centrifugation method were relatively smooth. Simultaneously, the flexural strength of denture base polymers was enhanced through centrifugation. Finally, no evident cytotoxic effects could be observed from different post-processing procedures. Clinical significanceThe centrifugation method could optimize surface quality and flexural strength of DLP-printed denture base polymers without compromising cytocompatibility, offering an alternative to conventional rinsing post-processing.

Regulation of nitrogen utilization and mycotoxin biosynthesis by the GATA transcription factor AaAreA in Alternaria alternata.

Alternaria alternata is a prevalent postharvest pathogen that generates diverse mycotoxins, notably alternariol (AOH) and alternariol monomethyl ether (AME), which are recurrent severe contaminants. Nitrogen sources modulate fungal growth, development, and secondary metabolism, including mycotoxin production. The GATA transcription factor AreA regulates nitrogen source utilization. However, little is known about its involvement in the regulation of nitrogen utilization in A. alternata. To examine the regulatory mechanism of AaAreA on AOH and AME biosynthesis in A. alternata, we analyzed the impact of diverse nitrogen sources on the fungal growth, conidiation and mycotoxin production. The use of a secondary nitrogen source (NaNO3) enhanced mycelial elongation and sporulation more than the use of a primary source (NH4Cl). NaNO3 favored greater mycotoxin accumulation than did NH4Cl. The regulatory roles of AaAreA were further clarified through gene knockout. The absence of AaAreA led to an overall reduction in growth in minimal media containing any nitrogen source except NH4Cl. AaAreA positively regulates mycotoxin biosynthesis when both NH4Cl and NaNO3 are used as nitrogen sources. Subcellular localization analysis revealed abundant nuclear transport when NaNO3 was the sole nitrogen source. The regulatory pathway of AaAreA was systematically revealed through comprehensive transcriptomic analyses. The deletion of AaAreA significantly impedes the transcription of mycotoxin biosynthetic genes, including aohR, pksI and omtI. The interaction between AaAreA and aohR, a pathway-specific transcription factor gene, demonstrated that AaAreA binds to the aohR promoter sequence (5'-GGCTATGGAAA-3'), activating its transcription. The expressed AohR regulates the expression of downstream synthase genes in the cluster, ultimately impacting mycotoxin production. This study provides valuable information to further understand how AreA regulates AOH and AME biosynthesis in A. alternata, thereby enabling the effective design of control measures for mycotoxin contamination.

Non‐Covalent Functionalization of Magnetic Carbon Nanotubes with Fmoc Amino Acid‐Modified Polyethylene Glycol

AbstractOnce dispersion and cytotoxicity issues are resolved, it has been proven that carbon nanotubes (CNTs) have great advantages in biomedical applications due to their unique properties. In this study, the superiority of carbon nanotubes was combined with magnetic targeting strategies, and a solution to the distribution problem in the aqueous media of the resulting CNTs decorated with iron oxide (mCNTs) was sought. A non‐covalent functionalization approach has been utilized to overcome this fundamental drawback of mCNTs. Conjugates of polyethylene glycol monomethyl ether and 9‐ fluorenyl methyl chloroformate (Fmoc) amino acids were used to coat the lateral surfaces of mCNTs, making them more water‐soluble. The selected Fmoc amino acids have different numbers of aromatic rings, which is known to affect the coating efficiency in non‐covalent functionalization and therefore, the dispersion behavior of the CNTs. Their coating yields, dispersion behaviors, magnetism, charge, and size properties have been determined. All coated mCNT samples displayed superparamagnetic behavior. Dispersion tests showed a promise to increase the stability of mCNTs with this approach. Moreover, we demonstrated that the functionalization of mCNTs affects cell viability in a dose‐dependent manner. The main finding of this study is that mCNTs can be successfully functionalized with Fmoc amino acid‐modified polyethylene glycol.

Tailored Metal-Porphyrin Based Molecular Electrocatalysts for Enhanced Artificial Nitrogen Fixation to Green Ammonia.

Electrochemical nitrogen reduction (E-NRR) is one of the most promising approaches to generate green NH3. However, scarce ammonia yields and Faradaic efficiencies (FE) still limit their use on a large scale. Thus, efforts are focusing on different E-NRR catalyst structures and formulations. Among present strategies, molecular electrocatalysts such as metal-porphyrins emerge as an encouraging option due to their planar structures which favor the interaction involving the metal center, responsible for adsorption and activation of nitrogen. Nevertheless, the high hydrophobicity of porphyrins limits the aqueous electrolyte-catalyst interaction lowering yields. This work introduces a new class of metal-porphyrin based catalysts, bearing hydrophilic tris(ethyleneglycol) monomethyl ether chains (metal = Cu(II) and CoII)). Experimental results show that the presence of hydrophilic chains significantly increases ammonia yields and FE, supporting the relevance of fruitful catalyst-electrolyte interactions. This study also investigates the use of hydrophobic branched alkyl chains for comparison, resulting in similar performances with respect to the unsubstituted metal-porphyrin, taken as a reference, further confirming that the appropriate design of electrocatalysts carrying peripheral hydrophilic substituents is able to improve device performances in the generation of green ammonia.