Amine Moiety Research Articles

Crystal structure of poly[(aceto-nitrile-κN)(μ3-7-{[bis-(pyridin-2-ylmeth-yl)amino]-meth-yl}-8-hy-droxy-quinoline-5-sulfonato-κ4N,O:O':O'')sodium

In the title compound, [Na(C22H19N4O4S)(CH3CN)]n, the NaI atom adopts a distorted square-pyramidal coordination geometry, formed by one N and one O atom of the qunolinol moiety in the ligand, two O atoms of sulfonate moieties of two adjacent ligands and the N atom of the coordinated aceto-nitrile solvent. The NaI atom is located well above the mean basal plane of the square-based pyramid. The apical position is occupied by a sulfonate O atom of a neighboring ligand. Three N atoms of the bis-(pyridin-2-ylmeth-yl)amine moiety in the ligand are not coordinated by the sodium atom. The mol-ecule forms an intra-molecular bifurcated O-H⋯[N(tertiary amine),N(pyridine)] hydrogen bond, generating S(6) and S(5) rings. In the crystal, four mol-ecules are linked by four Na-O(sulfonato) bridged coordination bonds, forming a supra-molecular centrosymmetric tetra-mer unit comprising an eight-membered ring, and generating a two-dimensional network sheet. The mol-ecules of different sheets form inter-molecular C-H⋯O hydrogen bonds, and thereby a three-dimensional network structure.

Zn(II)-complex-based hydrolytic nanozymes prepared by nanoprecipitation for the hydrolysis of carboxylic esters and methyl parathion

Zn(II)-complex-based nanozymes have been extensively used for the cleavage of carboxylic esters and phosphate esters. Cooperativity between neighboring Zn(II) complexes is of paramount importance for the development of Zn(II)-complex-based nanozymes with excellent efficiency. Here, we have developed a controllable synthetic strategy for the construction of Zn(II)-complex-based nanozymes by using the nanoprecipitation technique, which could bring Zn(II) complexes in close proximity and regulate their microenvironments. Linear copolymers containing di(2-picolyl)amine moieties were used for the preparation of Zn(II)-complex-based nanozymes by the coordination between di(2-picolyl)amine and Zn(II) ion. These Zn(II)-complex-based nanozymes displayed excellent catalytic performance in the hydrolysis of carboxylic esters. Moreover, hydrophobic Fe3O4 nanoparticles could be incorporated into Zn(II)-complex-based nanozymes via the one-step nanoprecipitation approach, enabling the recovery of nanozymes by using a permanent magnet. Such nanozymes effectively catalyzed the hydrolysis of methyl parathion, which is highly resistant to spontaneous hydrolysis and is extremely hazardous. These nanozymes may find application in the hydrolysis of hazardous carboxylic esters and phosphate esters.

Anti-viral, anti-bacterial, but non-cytotoxic nanocoating for reusable face mask with efficient filtration, breathability, and robustness in humid environment

We fabricated a multi-use face mask with anti-bacterial and anti-viral, but non-cytotoxic properties by adding a functional nanocoating on an electrospun nanofiber filter. The nanocoating consists of a copolymer synthesized from dimethyaminomethyl styrene (DMAMS) monomer containing anti-microbial tertiary amine moiety, and a biocompatible crosslinker, ethylene glycol dimethylacrylate (EGDMA). Initiated chemical vapor deposition process is utilized to deposit the nanocoating in order to impart desired functionalities conformally onto the nanofiber filter without deforming its highly porous structure. The synthesized non-cytotoxic copolymer of p(DMAMS-co-EGDMA), or pDE film showed excellent biocidal efficacy of > 99.995% and > 99.985% against Escherichia coli O157: H7 (E. coli O157: H7) and Staphylococcus aureus, respectively. The pDE-coated nanofiber filter shows a filtration efficiency of 91% with extremely low air resistance of ∼ 50 Pa. In highly humid conditions, the pDE-coated nanofiber filter shows long-term anti-microbial efficacy of 99.89% for E. coli O157: H7 up to 168 h, 99.21%, and 99.23% for human influenza virus (H1N1) strain A/Puerto Rico/8/1934 and human beta-coronavirus strain OC43 up to 100 h, without sacrificing breathability, and filtration performance. Furthermore, the surface-modified filter can easily eliminate dead pathogens with a simple water rinse, which enabled the full retention of the filtration efficiency even in six washing cycles, proving excellent reusability. We envision the highly breathable, antimicrobial, multi-use face mask will serve as an environmentally free platform for personal protective equipment against future viral threats.

Gas-Phase Internal Proton-Transfer of Protonated para-Aminobenzoic Acid Catalyzed by One Methanol Molecule.

Electrospray ionization (ESI) is used to deliver analytes for mass analysis across a huge range of mass spectrometry applications. Despite its ubiquitous application and many mechanistic investigations, it remains that a fundamental understanding of ESI processes is not complete. In particular, all the factors that influence the populations of protonation isomers are elusive such that it remains a challenge to optimize experimental conditions to favor one isomer over another. The molecule para-aminobenzoic acid has emerged as an archetype for the study of protonation isomers, with both amino and carboxylic acid protonation site isomers (protomers) typically formed upon ESI, with the isomer ratio shown to be sensitive to several physical and chemical parameters. Here we report an ion-trap mass spectrometry study of the time-resolved methanol-catalyzed proton transfer between the amine and carboxylic acid moieties of para-aminobenzoic acid. The experimental and computational results presented are consistent with a bimolecular mechanism where isomerization is mediated by a single methanol rather than a multimolecular Grotthuss proton transfer process. Pseudo-first-order rate constants for protomer specific product ions are reported and confirm the depletion of the amino protomer is correlated to the growth of the carboxylic acid protomer. Under the controlled conditions of a low-pressure ion-trap mass spectrometer (2.5 mTorr, 300 K), the number of methanol molecules required to isomerize para-aminobenzoic acid is determined to be one, and the second-order rate constant for methanol-catalyzed isomerization is (1.9 ± 0.1) × 10-11 cm3 molecule-1 s-1. The para-aminobenzoic acid vehicle mechanism is explored computationally at the DSD-PBEP86-D3BJ/aug-cc-pVDZ level of theory and reveals that the transition state for proton transfer is submerged (-10 kJ mol-1) relative to the separated reactant energies. The findings from this paper show that single-solvent catalyzed intramolecular proton transfer reactions are possible and must be considered during the late stages of ESI to predict the site(s) of protonation and the ion's stability in the presence of solvent molecules.

Process Development and Scale-Up of the SOS1 Inhibitor MRTX0902

MRTX0902, a novel SOS1 inhibitor, is currently being evaluated in phase I trials for the treatment of cancer. The complexity of the molecule, which contains a pyrido[3,4-d]pyridazine core and a chiral amine moiety, makes it a challenging target to prepare on a multi-kilogram scale to support clinical development studies. An efficient and scalable synthesis of the key intermediate 4-methyl-7-morpholinopyrido[3,4-d]pyridazin-1(2H)-one and a much improved end-game for MRTX0902 were developed.

Optimization, and biological evaluation of 3-O-β-chacotriosyl betulinic acid amide derivatives as novel small-molecule Omicron

SARS-CoV-2 Omicron viruses possess a high antigenic shift, and the approved anti-SARS-CoV-2 drugs are extremely limited, which makes the development of new antiviral drugs for the clinical treatment and prevention of SARS-CoV-2 outbreaks imperative. We have previously discovered a new series of markedly potent small-molecule inhibitors of SARS-CoV-2 virus entry, exampled by the hit compound 2. Here, we report a further study of bioisosteric replacement of the eater linker at the C-17 position of 2 with a variety of aromatic amine moieties, followed by a focused structure-activity relationship study, leading to the discovery of a series of novel 3-O-β-chacotriosyl BA amide derivatives as small-molecule Omicron fusion inhibitors with improved potency and selectivity index. Particularly, our medicinal chemistry efforts have resulted in a potent, and efficacious lead compound S-10 with appreciable pharmacokinetic properties, which exhibited broad-spectrum potency against Omicron and other variants with EC50 values ranging from 0.82 to 5.45 μM. Mutagenesis studies confirmed that inhibition of Omicron viral entry was mediated by the direct interaction with S in the prefusion state. These results reveal that S-10 is suitable for further optimization as Omicron fusion inhibitors, with the potential to be developed as therapeutic agents for the treatment and control of SARS-CoV-2 ant its variants infections.

Development of Sٍٍensitive Spectrofluorimetric Methods for Determining Netilmicin Based on Selective Condensation Reactions of its Amine Moiety with each Acetylacetone/Formaldehyde and Ninhydrin/Phenylacetaldehyde Reagents

Netilmicin is an aminoglycoside antibiotic used to treat infections caused by a broad spectrum of Gram-negative and Gram-positive bacteria and is pharmaceutically formulated in ophthalmic dosage forms. In this study, two spectrofluorimetric approaches were designed and developed to switch-on the fluorescence activity of NTC. The first method, or Hantzsch (HNZ) method, was relied on measuring the generated fluorescence intensity upon the condensation of NTC with acetylacetone and formaldehyde (Hantzsch reaction) at λemis=483 nm/λexcit=425.5 nm. While the second fluorometric method (NHD method) was relied on measuring the generated fluorescence intensity upon the condensation of NTC with ninhydrin/phenylacetaldehyde at λemis=482.2 nm/λexcit=385.8 nm. The reaction conditions for the two approaches were well investigated and optimized. The selectivity study for the methods was investigated by determining NTC in the presence of the co-formulated drug (dexamethasone) and pharmaceutical excipients. The validation for two approaches was performed based on ICH guidelines, and ranges of linearity were 0.1-1.2 and 1.5-6.0 µg/mL, while LOD values were 0.039 and 0.207 µg/mL for the HNZ method and the NHD method, respectively. Finally, NTC has been determined in different ophthalmic preparations by the proposed approaches with adequate recovery values.

Cover Feature: Impact of Structural Flexibility of Amine Moieties as Bridges for Redox‐Active Sites on Secondary Battery Performance (ChemSusChem 10/2023)

The Cover Feature shows two organic compounds, 3-dithione-diamine and 3-dithione-amine, as organic cathode candidates for secondary batteries in this study. The study highlights that the 3-dithione-diamine, located in the bottom left corner and known for its structural robustness, demonstrates cyclic durability and electrochemical performance comparable to the structurally flexible 3-dithione-amine. More information can be found in the Research Article by S. Choi et al.

Mercaptoamine-assisted Post-encapsulation of Metal Nanoparticles within Preformed Zeolites and their Analogues for Hydroisomerization and Methane Decomposition.

We report a general synthetic strategy for post-encapsulation of metal nanoparticles within preformed zeolites using post-synthetic modification. Both anionic and cationic precursors to metal nanoparticle are supported on 8- and 10-membered ring zeolites and analogues during wet impregnation using 2-aminoethanethiol (AET) as a bi-grafting agent. Thiol groups are coordinated to metal centers, whereas amine moieties are dynamically attached to micropore walls via acid-base interactions. The dynamic acid-base interactions cause the even distribution of the metal-AET complex throughout the zeolite matrix. These processes encapsulate Au, Rh, and Ni precursors within the CHA, *MRE, MFI zeolite, and SAPO-34 zeolite analogues, for which small channel apertures preclude the post-synthesis impregnation of metal precursors. Sequential activation forms small and uniform nanoparticles (1-2.5 nm in diameter), as confirmed through electron microscopy and X-ray absorption spectroscopy. Containment within the small micropores protected the nanoparticles against harsh thermal sintering conditions and prevented the fouling of the metal surface by coke, thus resulting in a high catalytic performance in n-dodecane hydroisomerization and methane decomposition. The remarkable specificity of the thiol to metal precursors and the dynamic acid-base interaction make these protocols extendable to various metal-zeolite systems, suitable for shape-selective catalysts in challenging chemical environments.

Mercaptoamine‐assisted Post‐encapsulation of Metal Nanoparticles within Preformed Zeolites and their Analogues for Hydroisomerization and Methane Decomposition

AbstractWe report a general synthetic strategy for post‐encapsulation of metal nanoparticles within preformed zeolites using post‐synthetic modification. Both anionic and cationic precursors to metal nanoparticle are supported on 8‐ and 10‐membered ring zeolites and analogues during wet impregnation using 2‐aminoethanethiol (AET) as a bi‐grafting agent. Thiol groups are coordinated to metal centers, whereas amine moieties are dynamically attached to micropore walls via acid‐base interactions. The dynamic acid‐base interactions cause the even distribution of the metal‐AET complex throughout the zeolite matrix. These processes encapsulate Au, Rh, and Ni precursors within the CHA, *MRE, MFI zeolite, and SAPO‐34 zeolite analogues, for which small channel apertures preclude the post‐synthesis impregnation of metal precursors. Sequential activation forms small and uniform nanoparticles (1–2.5 nm in diameter), as confirmed through electron microscopy and X‐ray absorption spectroscopy. Containment within the small micropores protected the nanoparticles against harsh thermal sintering conditions and prevented the fouling of the metal surface by coke, thus resulting in a high catalytic performance in n‐dodecane hydroisomerization and methane decomposition. The remarkable specificity of the thiol to metal precursors and the dynamic acid‐base interaction make these protocols extendable to various metal‐zeolite systems, suitable for shape‐selective catalysts in challenging chemical environments.

Molecular dynamics simulation of ssDNA and cationic polythiophene

In this work, molecular dynamics simulations of complexes composed of single strand DNA (ssDNA) sequences and cationic oligothiophenes are performed to understand experimental findings and the sensing ability of polythiophene electrolytes toward ssDNA. The simulation results exhibit no significant structural effect for replacing the cationic amine moiety with imidazole derivative on the side group of the oligomer. Adding a homopurine strand elongates the oligomer backbone; on the contrary, mixing up the homopyrimidine strand causes compression. On the other hand, these ssDNAs do not notably affect the compactness of the oligomer backbones. The anion-cation interactions play an essential role in the structural and spectroscopic change of cationic polythiophenes (CPTs) upon complexation with ssDNAs. The red shift of CPTs in the UV-VIS spectra with the addition of homopurine strands might be explained by the strong anion-cation, weak π −cation interactions, and high binding affinities. Nonpolar interactions (vdW and SA) and complex solvation energies dominate binding free energies. Hydrogen interaction analyses show that oligomers most likely approach the ssDNAs from their backbone upon complexation except for the duplex containing homopyrimidine strand and oligothiophene possessing imidazole derivative side chain.

An Engineered Nanosugar Enables Rapid and Sustained Glucose‐Responsive Insulin Delivery in Diabetic Mice (Adv. Mater. 21/2023)

Insulin Delivery In article number 2210392, Christoph E. Hagemeyer, Francesca Cavalieri, and co-workers report how biodegradable and charge-switchable phytoglycogen nanoparticles with glucose-sensitive phenylboronic acid groups and amine moieties can be engineered to form nanocomplexes with insulin for its rapid and efficient glucose-responsive delivery. Subcutaneous injection of nanocomplexes in two distinct diabetic mouse models helps to maintain normal glucose levels for up to 13 h.

An ultrahigh permeance and CO2 selective membrane of organosilica-based coordination polymer tailored via nickel crosslinking

A novel concept that involves the use of an organosilica-based coordination polymer was successfully implemented to create a high-performance nickel-dope-hindered tertiary amine-ring structure in tris-(trimethoxysilyl propyl) isocyanurate silane (TTPI) membranes for CO2/N2 separation. The interfacial crosslinking was developed from nickel (Ni) metal sites that served as Lewis-acid molecules with amine moieties from isocyanurate-ring as Lewis-base molecules. We discovered that high levels of nickel/amine (Ni/N) mole ratios improves metal affinity, thus enhancing the structural rigidity, surface area (from 30.1 to 308 m2 g−1), and improves the CO2 adsorption capacity of Ni-TTPI membranes, which results in high levels of gas permeance on the order of Ni-TTPI 0.25 > Ni-TTPI 0.125 > TTPI. In addition, we found that the CO2 separation performance of Ni-TTPI membranes is also influenced by nickel-amine coordination and that Ni(OH)2 facilitates adsorption at a calcination temperature of 250 °C. An ultrahigh CO2 permeance of 3 × 10−6 mol m−2 s−1 Pa−1 (8,960 GPU) and a CO2/N2 permeance ratio of 40 was achieved in a CO2/N2 (1/9) mixture of Ni-TTPI at the highest Ni/N ratio of 0.25 mol mol−1 due to precise tuning of the pore size, increased microporosity, and the establishment of Ni(OH)2, which results in lower activation energy for CO2, which indicates great potential for permeation.

Ozonation of Gabapentin in Water─Investigating Reaction Kinetics and Transformation Mechanisms of a Primary Amine Using Isotopically Labeled Ozone.

Aliphatic amines are abundant micropollutants in wastewater treatment plant effluents. In order to mitigate such micropollutants, ozonation is one of the most commonly employed advanced treatment processes. Current research regarding ozone efficiency is heavily focusing on reaction mechanisms of different contaminant groups, including structures with amine moieties as reactive sites. This study analyzes pH-dependent reaction kinetics and pathways of gabapentin (GBP), an aliphatic primary amine with an additional carboxylic acid group. The transformation pathway was elucidated applying a novel approach using isotopically labeled ozone (18O) and quantum chemistry calculations. While the direct reaction of GBP with ozone is highly pH-dependent and slow at pH 7 (13.7 M-1 s-1), the rate constant of the deprotonated species (1.76 × 105 M-1 s-1) is comparable to those of other amine compounds. Pathway analysis based on LC-MS/MS measurements revealed that ozonation of GBP leads to the formation of a carboxylic acid group and simultaneous nitrate formation, which was also observed in the case of the aliphatic amino acid glycine. Nitrate was formed with a yield of approximately 100%. Experiments with 18O-labeled ozone demonstrated that the intermediate aldehyde does most likely not include any oxygen originating from ozone. Furthermore, quantum chemistry calculations did not provide an explanation for the C-N scission during GBP ozonation without ozone involvement, although this reaction was slightly more favorable than for respective glycine and ethylamine reactions. Overall, this study contributes to a deeper understanding of reaction mechanisms of aliphatic primary amines during wastewater ozonation.

Impact of Structural Flexibility of Amine Moieties as Bridges for Redox-Active Sites on Secondary Battery Performance.

Although environmentally benign organic cathode materials for secondary batteries are in demand, their high solubility in electrolyte solvents hinders broad applicability. In this study, a bridging fragment to link redox-active sites is incorporated into organic complexes with the aim of preventing dissolution in electrolyte systems with no significant performance loss. Evaluation of these complexes using an advanced computational approach reveals that the type of redox-active site (i. e., dicyanide, quinone, or dithione) is a key parameter for determining the intrinsic redox activity of the complexes, with the redox activity decreasing in the order of dithione>quinone>dicyanide. In contrast, the structural integrity is strongly reliant on the bridging style (i. e., amine-based single linkage or diamine-based double linkage). In particular, owing to their rigid anchoring effect, diamine-based double linkages incorporated at dithione sites allow structural integrity to be maintained with no significant decrease in the high thermodynamic performance of dithione sites. These findings provide insights into design directions for insoluble organic cathode materials that can sustain high performance and structural durability during repeated cycling.

Molecular Design of Asymmetric Cyclophosphamide as Electrolyte Additive for High-Voltage Lithium-Ion Batteries

Elevating the charging voltage could greatly promote the energy density of lithium-ion batteries (LIBs) with LiNixMnyCozO2 cathodes, although challenges arise from severe parasitic reactions and rapid capacity decay at high voltage, especially for nickel-rich cathodes. Herein, by incorporating various useful functionalities into one single molecule, we rationally design and synthesize a new class of five-membered asymmetric cyclophosphamides as electrolyte additives to enable stable cycling of high-voltage LIBs. It is demonstrated that the strong Lewis-base feature of the P–N bond can effectively scavenge the detrimental HF and H2O in the electrolyte. Meanwhile, the five-membered ring with an asymmetric amine moiety undergoes ring-opening polymerization to generate a highly robust and thin polymeric cathode–electrolyte interphase. Benefiting from the above merits, the asymmetric cyclophosphamide additive significantly suppresses decomposition of the electrolyte, dissolution of the transitional metals, and structural damage to the cathode, thus markedly improving the cycling stability and Coulombic efficiency of both high-voltage coin and pouch LIBs (up to 4.6 V).

Tuning fluorescence of dapoxetine by blocking of photoinduced electron transfer (PET): Application in real human plasma.

Photoinduced electron transfer (PET) is the most common mechanism proposed to account for quenching of fluorophores. Herein, the intrinsic fluorescence of dapoxetine (DPX) hydrochloride is in the "OFF" state, owing to the deactivation effect of PET. When the amine moiety is protonated, the fluorescence is restored. Protonation of the nitrogen atom of the tertiary amine moiety in DPX leads to "ON" state of fluorescence due to hindrance of the deactivating effect of PET by protonation of the amine moiety. This permits specific and sensitive determination of DPX in human plasma [lower limit of quantification (LLOQ) = 30.0 ]. The suggested method adopts protonation of DPX using 0.25 M hydrochloric acid in anionic micelles [6.94 mM sodium dodecyl sulfate (SDS)] leads to a marked enhancement of DPX-fluorescence, after excitation at 290 nm.

Nitrifying Microorganisms Linked to Biotransformation of Perfluoroalkyl Sulfonamido Precursors from Legacy Aqueous Film-Forming Foams.

Drinking water supplies across the United States have been contaminated by firefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much of the AFFF is manufactured using electrochemical fluorination by 3M. Precursors with six perfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third of the PFAS in 3M AFFF. C6 precursors can be transformed through nitrification (microbial oxidation) of amine moieties into perfluorohexane sulfonate (PFHxS), a compound of regulatory concern. Here, we report biotransformation of the most abundant C6 sulfonamido precursors in 3M AFFF with available commercial standards (FHxSA, PFHxSAm, and PFHxSAmS) in microcosms representative of the groundwater/surface water boundary. Results show rapid (<1 day) biosorption to living cells by precursors but slow biotransformation into PFHxS (1-100 pM day-1). The transformation pathway includes one or two nitrification steps and is supported by the detection of key intermediates using high-resolution mass spectrometry. Increasing nitrate concentrations and total abundance of nitrifying taxa occur in parallel with precursor biotransformation. Together, these data provide multiple lines of evidence supporting microbially limited biotransformation of C6 sulfonamido precursors involving ammonia-oxidizing archaea (Nitrososphaeria) and nitrite-oxidizing bacteria (Nitrospina). Further elucidation of interrelationships between precursor biotransformation and nitrogen cycling in ecosystems would help inform site remediation efforts.

Probing radical versus proton migration in the aniline cation with IRMPD spectroscopy

Intramolecular radical and proton migration in the gas phase are important processes driving the dissociation reactions underlying common tandem mass spectrometry processes, such as collision-induced and electron-induced dissociation reactions (CID and ExD). Mechanistic insights in these processes requires experiments that probe the molecular structures of ions along the reaction pathways, usually combined with quantum-chemical calculations. The combination of ion trap mass spectrometry with IR laser spectroscopy, pioneered among others by Dieter Gerlich, provides a particularly effective method to explore details of the ion structures. In this work, we employ infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations to probe the reactant and product ion structures of a homolytic bond cleavage reaction. First, we employ IRMPD spectroscopy to establish that protonation of the 4-bromoaniline precursor occurs on the amine moiety and then that C-Br homolytic cleavage produces the π-radical cation of aniline. Transition-state calculations are performed to compare the various pathways that connect reactant and product ions, including both proton and radical transfer mechanisms.

Multifunctional polymer electrolyte membrane networks for energy storage via ion-dipole complexation in lithium metal battery

A novel concept of energy storage is presented involving ion-dipole complexation within multifunctional polymer electrolyte membrane (PEM), consisting of polyethylene glycol diacrylate (PEGDA) and succinonitrile (SCN) plasticizer and lithium bis-trifluoromethane sulfonyl imide (LiTFSI) salt. A similar complexation of lithium ions with ether oxygen and amine moieties occurs in the thermally cured poly(ethylene glycol) diglycidyl ether (PEGDGE) - polyether amine (Jeffamine D400, 2-arm) co-network. By virtue of the network functional groups, the ion transport is hindered which may be viewed as temporally holding of the Li ions, reminiscent of ion storage. Although some Li ions may be partially immobilized due to ion-dipole complexation, upon prelithiation via deep discharging the lithium metal/PEM/lithium iron phosphate (LFP) battery assembly to the low potential range of 0.01–0.5 V (i.e., oxidation at the Li metal anode), excess mobile Li ions become available that can travel to the cathode through the Li+ saturated complexation sites at ease, exhibiting high ionic conductivity with energy storage capability within the PEM matrix. Another way of supplying Li ions to PEM is through diffusion driven by ion concentration gradient between the two-layer PEM composite composed of a high salt concentration layer and a no-salt layer. The CV measurement was carried out as a function of aging time on the bilayer composite in the PEM potential range of 0.01 to 2.5 V, which indeed revealed a systematic emergence of redox reaction peaks, thereby validating the energy storing concept of the multifunctional PEM network.