Additional Free Energy Research Articles

Dissolution of Primary Carbides and Formation and Healing of Kirkendall Voids in Bearing Steel under Pulsed Electric Current

The alloying elements in 8Cr4Mo4V bearing steel tend to form large primary carbides with carbon, which not only causes element segregation but also becomes the primary source of fatigue crack initiation, thereby decreasing the material's usability and machinability. Owing to the excellent thermal stability of primary carbides, traditional homogenization annealing requires high temperatures, which is both time‐ and energy‐intensive. Excessively high heat treatment temperatures can also result in “overburning” of the sample. Herein, primary carbides are rapidly dissolved at low temperatures using pulsed electric current treatment. The additional free energy introduced by the pulsed electric current lowers the thermodynamic barrier for carbide dissolution. During the second‐phase dissolution process, the unbalanced diffusion of elements may cause the formation of Kirkendall voids. Due to the difference in electrical conductivity between the voids and the matrix, the pulsed electric current generates thermal compressive stress on the voids, promoting rapid atom migration to these voids and accelerating their healing. This pulse‐current treatment technology offers a novel method for the rapid dissolution of carbides in alloys at low temperatures and for the rapid healing of related voids.

The genetic architecture of protein stability

There are more ways to synthesize a 100-amino acid (aa) protein (20100) than there are atoms in the universe. Only a very small fraction of such a vast sequence space can ever be experimentally or computationally surveyed. Deep neural networks are increasingly being used to navigate high-dimensional sequence spaces1. However, these models are extremely complicated. Here, by experimentally sampling from sequence spaces larger than 1010, we show that the genetic architecture of at least some proteins is remarkably simple, allowing accurate genetic prediction in high-dimensional sequence spaces with fully interpretable energy models. These models capture the nonlinear relationships between free energies and phenotypes but otherwise consist of additive free energy changes with a small contribution from pairwise energetic couplings. These energetic couplings are sparse and associated with structural contacts and backbone proximity. Our results indicate that protein genetics is actually both rather simple and intelligible.

Computational Screening of Hydrophobic Zeolites for the Removal of Emerging Organic Contaminants from Water.

The pollution of water resources by pharmaceuticals and agents of personal care products (PPCPs) poses an increasingly pressing issue that has received considerable attention from scientists and government agencies alike. Hydrophobic zeolites can serve as selective adsorbents to remove these contaminants from aqueous solution. So far, the adsorption of PPCPs in zeolites has often been investigated in case studies focusing on a small number of contaminants and one or a few zeolites. We present a computational screening approach to investigate the interaction of 53 PPCPs with 14 all-silica zeolites, aiming at a more comprehensive understanding of factors that are beneficial for a strong host-guest interaction and thus an efficient adsorption. The systems are modelled on the classical force field level of theory, allowing for the efficient computational treatment of a large number of PPCP-zeolite combinations and evaluated in terms of the interaction energy between PPCP and zeolite framework. For selected PPCP-zeolite combinations additional Free Energy Perturbation simulations are employed to compute Free Energies of Transfer between the aqueous phase and the adsorbed state. These results can serve as a starting point for experimental studies of relevant PPCP-zeolite combination or more in-depth theoretical investigations.

Accelerated precipitation and enhanced mechanical properties of Cu-3.5Ti alloy via electropulsing treatment

Aging is an important step in improving the comprehensive properties of Cu-3.5Ti alloy. However, both prolonged holding times and high heat treatment temperatures lead to significant oxidation and substantial energy consumption. The effects of heat treatment (HT) and electropulsing treatment (EPT) on the microstructure and mechanical properties of the solid solution Cu-3.5Ti alloy were comparatively examined in this study. The findings demonstrated that EPT quickly completed the processes of spinodal decomposition and short-range ordered to long-range ordered phase transformation, thereby fully precipitating fine and diffusive β′-Cu4Ti phase, which greatly enhanced the precipitation strengthening effects. In addition to enhancing the strength of the alloy, EPT significantly reduced the peak aging time (to just 1/12 of that of HT) and greatly increased the plasticity (elongation to failure rose by 47 % compared to HT). The main reason for the rapid completion of the spinodal decomposition and the full precipitation process by the EPT was the additional free energy provided by the electropulsing, which significantly accelerated the Ti atomic diffusion and lowered the nucleation barrier of the β′-Cu4Ti phase. EPT is a toughening heat treatment process for metallic materials, which offers the advantages of high efficiency, low energy consumption, and low cost.

A Molecular Expression for "Line Tension".

"Line tension", a concept that features in an additional term to the Young's equation, was introduced to describe the size dependence of contact angles of nanodroplets on surfaces. Although this concept describes the observations in a succinct, elegant manner, theorists have long had misgivings about the physical interpretation of the phenomenon. Papers have been published that attempt to nail down its value, which is reportedly very small (∼10 pN) and evidently even the sign has been uncertain. Attempts to interpret it in a mechanical manner analogous to interfacial tension, i.e., due to the curvature of the three-phase contact line, have run into conceptual problems that require invocations of ever more complex models. In this work, we have used molecular simulations to systematically relate "line tension" to the additional free energy per unit length of the three-phase line and found no direct relation. However, when we rederived the Young's equation without ignoring the interfacial molecules, we found a physically satisfying explanation for the size dependence of the contact angle of nanodroplets without invoking the curvature of the three-phase contact line. The new model does not have the elegant form of the modified Young's equation, but each parameter in it has an unambiguous physical interpretation. An approximate form of this model, linearized in the inverse droplet radius, yields a quantity that is mathematically analogous to what is conventionally called "line tension", but unpacked at the molecular level, showing that it is unrelated to a restoring force associated with the curvature of the macroscopic three-phase contact line.

Elucidating the Molecular Determinants of the Binding Modes of a Third-Generation HIV-1 Integrase Strand Transfer Inhibitor: The Importance of Side Chain and Solvent Reorganization.

The first- and second-generation clinically used HIV-1 integrase (IN) strand transfer inhibitors (INSTIs) are key components of antiretroviral therapy (ART), which work by blocking the integration step in the HIV-1 replication cycle that is catalyzed by a nucleoprotein assembly called an intasome. However, resistance to even the latest clinically used INSTIs is beginning to emerge. Developmental third-generation INSTIs, based on naphthyridine scaffolds, are promising candidates to combat drug-resistant viral variants. Among these novel INSTIs, compound 4f exhibits two distinct conformations when binding with intasomes from HIV-1 and the closely related prototype foamy virus (PFV) despite the high structural similarity of their INSTI binding pockets. The molecular mechanism and the key active site residues responsible for these differing binding modes in closely related intasomes remain elusive. To unravel the molecular determinants governing the two distinct binding modes, we applied a novel molecular dynamics-based free energy method that utilizes alchemical pathways to overcome the sampling challenges associated with transitioning between the two bound conformations of ligand 4f within the crowded environments of the INSTI binding pockets in these intasomes. The calculated conformational free energies successfully recapitulate the experimentally observed binding mode preferences in the two viral intasomes. Analysis of the simulated structures suggests that the observed binding mode preferences are caused by amino acid residue differences in both the front and the central catalytic sub-pocket of the INSTI binding site in HIV-1 and PFV. Additional free energy calculations on mutants of HIV-1 and PFV revealed that while both sub-pockets contribute to binding mode selection, the central sub-pocket plays a more important role. These results highlight the importance of both side chain and solvent reorganization, as well as the conformational entropy in determining the ligand binding mode, and will help inform the development of more effective INSTIs for combatting drug-resistant viral variants.

Isogeometric smooth crack-band model (isCBM) using spress–sprain relations adapted to microplane theory

Recent optimum fitting of the data from eleven different types of distinctive fracture tests of quasibrittle materials, including the gap tests and the size effect tests, revealed that the crack band model (CBM) with the M7 damage constitutive law outperforms all the other existing computational fracture models for concrete. This is attributed to physically correct boundary conditions, especially those at the crack faces,to the crack front of finite width which allows using a triaxial tensorial damage constitutive law, and to choosing for this law a realistic material behavior description, the M7. Nevertheless the CBM has limitations—the width of the crack band cannot be varied, the statistically smooth damage distribution across the band cannot be resolved, and the propagation direction is biased by the mesh orientation when a regular mesh is used. These limitations have been overcome by the smooth crack band model (sCBM), which uses unconventional homogenization of damage mechanics to yield an additional Helmholtz free energy density, called the “sprain energy”. This energy is a function of the curvature tensor (or a hessian) of the vectorial displacement field, called the “sprain curvature tensor” (or sprain tensor for brevity), which is a sum of the strain gradient tensor and, importantly, the rotation gradient tensor. But, in a previous study, difficulties arose in computational implementation—the use of constant-strain elements required the curvature to be resisted by sprain forces that represented the derivatives of sprain energy with respect to nodal displacements and had to be applied on the nodes of adjacent elements. The need for adjacent nodes is here avoided by a variational derivation of the Isogeometric Smooth Crack-Band Model (isCBM). The microplane damage constitutive model M7 for concrete is adopted, which is made possible by establishing the relations of the sprain stress (or spress, for brevity) and sprain on microplanes of arbitrary orientations. Using Isogeometric Analysis (IGA) based on non-uniform rational B-Splines (NURBS), the excessive displacement curvature and its resistance (spress) can be described by the shape functions with C1-continuity. Computational results show that the orientation bias of regular meshes is eliminated while keeping the constitutive law intact, which is important for compatibility with the existing material laws in general. In addition, comparisons with experimental data reveal that isCBM with M7 can reproduce the correspondence between the size of the fracture process zone and the fracture energy, as indicated by gap tests. Finally, the isCBM does not compromise the strain-path-dependence of material response.

A Phenylboronic Acid-Based Transition State Analogue Yields Nanomolar Inhibition of Mandelate Racemase.

Mandelate racemase (MR) catalyzes the Mg2+-dependent interconversion of (R)- and (S)-mandelate by stabilizing the altered substrate in the transition state (TS) by ∼26 kcal/mol. The enzyme has been employed as a model to explore the limits to which the free energy of TS stabilization may be captured by TS analogues to effect strong binding. Herein, we determined the thermodynamic parameters accompanying binding of a series of bromo-, chloro-, and fluoro-substituted phenylboronic acids (PBAs) by MR and found that binding was predominately driven by favorable entropy changes. 3,4-Dichloro-PBA was discovered to be the most potent inhibitor yet identified for MR, binding with a Kdapp value of 11 ± 2 nM and exceeding the binding of the substrate by ∼72,000-fold. The ΔCp value accompanying binding (-488 ± 18 cal·mol-1 K-1) suggested that dispersion forces contribute significantly to the binding. The pH-dependence of the inhibition revealed that MR preferentially binds the anionic, tetrahedral form of 3,4-dichloro-PBA with a pH-independent Ki value of 5.7 ± 0.5 nM, which was consistent with the observed upfield shift of the 11B NMR signal. The linear free energy relationship between log(kcat/Km) and log(1/Ki) for wild-type and 11 MR variants binding 3,4-dichloro-PBA had a slope of 0.8 ± 0.2, indicating that MR recognizes the inhibitor as an analogue of the TS. Hence, halogen substitution may be utilized to capture additional free energy of TS stabilization arising from dispersion forces to enhance the binding of boronic acid inhibitors by MR.

Stimulating the inverse transformation of amorphous second-phase particles in irradiated Zr alloy to modulate the nanostructure

Amorphization of the second phase particles in irradiated zirconium alloys tends to lead to defect formation, radiation growth and corrosion resistance reduction, while conventional annealing requires higher temperature to promote amorphous crystallization transformation, which may reduce the performance of materials. Based on the difference of electrical properties between the second phase particles and the matrix, the pulsed electric current can induce the crystallization of amorphous second phase particles at a lower temperature by introducing additional electrical free energy, so as to achieve the microregion regulation of materials. The pulsed electric current effectively reduces the recrystallization activation energy of the second phase particles from 96 kJ/mol to 63.68 kJ/mol, thus lowering the recrystallization barrier to accelerate its process. The proposed pulsed electric current can rapidly reverse the crystal structure of amorphous second phase particles at lower temperatures, which provides a novel idea for adjusting the microstructure of metal materials.

Study on in situ visualization crystallization behavior and secondary nucleation model of polypropylene under supercritical N2

The crystal morphology and crystallization kinetics of polymers under supercritical N2 have an important impact on the polymers’ melt strength as well as the microstructure and properties of microcellular plastic parts. Herein, the self-made in-situ high pressure microscopy system was employed to study the spherulite morphology and crystal growth behavior in high pressure N2. It was found that PP spherulites were significantly refined under supercritical N2. As the N2 pressure was augmented to 20.69 MPa at 130 °C, the spherulite size was reduced to 48.41 μm, refined by 35.84%, indicating that the crystallization behavior of PP can be controlled by pressure regulation. The new growth pattern for spherulite under supercritical N2 was discovered by atomic force microscope (AFM) for the first time. In addition, the spherulite growth rate exhibited a phenomenon that was inhibited first and then promoted. To explore the re-promoting effect of supercritical N2, a secondary nucleation model that considered the effect of additional free energy induced by high-pressure N2, was established. The re-promotion of spherulite growth rate at elevated N2 pressure is attributed to the augment in translational free energy induced by N2, i.e., entropy-driven crystallization. The calculated results of secondary nucleation model achieved a good agreement with the experimental results, and the variation trend of PP spherulite growth rate could be well predicted under supercritical N2.

Transport barrier onset and edge turbulence shortfall in fusion plasmas

Magnetic confinement fusion offers the promise of sustainable and safe energy production on Earth. Advanced experimental scenarios exploit the fascinating yet uncommon ability of confined plasmas to bifurcate into states of enhanced performance upon application of additional free energy sources. Self-regulation of small-scale turbulent eddies is essential to accessing these improved regimes. However, after several decades, basic principles for these bifurcations are still largely debated and clarifications from first principles lacking. We show here, computed from the primitive kinetic equations, establishment of a state of improved confinement through self-organisation of plasma microturbulence. Our results highlight the critical role of the interface between plasma and material boundaries and demonstrate the importance of propagation of turbulence activity beyond regions of convective drive. These observations strongly suggest a paradigm shift where the magnetised plasma at the onset of enhanced performance self-organises into a globally critical state, ‘nonlocally’ controlled by fluxes of turbulence activity.

Superhydrophobic Coating Based on Porous Aluminum Oxide Modified by Polydimethylsiloxane (PDMS).

The aim of this study was to obtain a superhydrophobic coating by modifying anodized aluminum using polydimethylsiloxane (PDMS). In order to obtain a superhydrophobic coating on an aluminum substrate, a multistage treatment was implemented. Specimens of aluminum were treated by abrasive blasting, anodization in sulfuric acid, impregnation by PDMS, rinsing in toluene to remove excess of PDMS, and curing. A rough surface with an additional low free energy layer on it resulted in a superhydrophobic effect. The coating obtained has an average contact angle of 159°. The specimens were tested in terms of durability in natural conditions. Additionally, anti-icing and anti-fouling properties were evaluated. The coating was compared with anodized aluminum obtained by a basic process.

Nonexponential kinetics captured in sequential unfolding of polyproteins over a range of loads.

While performing under mechanical loads in vivo, polyproteins are vitally involved in cellular mechanisms such as regulation of tissue elasticity and mechano-transduction by unfolding their comprising domains and extending them. It is widely thought that the process of sequential unfolding of polyproteins follows an exponential kinetics as the individual unfolding events exhibit identical and identically distributed (iid) Poisson behavior. However, it was shown that under high loads, the sequential unfolding kinetics displays nonexponential kinetics that alludes to aging by a subdiffusion process. Statistical order analysis of this kinetics indicated that the individual unfolding events are not iid, and cannot be defined as a Poisson (memoryless) process. Based on numerical simulations it was argued that this behavior becomes less pronounced with lowering the load, therefore it is to be expected that polyproteins unfolding under lower forces will follow a Poisson behavior. This expectation serves as the motivation of the current study, in which we investigate the effect of force lowering on the unfolding kinetics of Poly-L8 under varying loads, specifically high (150, 100 ​pN) and moderate-low (45, 30, 20 ​pN) forces. We found that a hierarchy among the unfolding events still exists even under low loads, again resulting in nonexponential behavior. We observe that analyzing the dwell-time distributions with stretched-exponentials and power laws give rise to different phenomenological trends. Using statistical order analysis, we demonstrated that even under the lowest load, the sequential unfolding cannot be considered as iid, in accord with the power law distribution. Additional free energy analysis revealed the contribution of the unfolded segments elasticity that scales with the force on the overall one-dimensional contour of the energy landscape, but more importantly, it discloses the hierarchy within the activation barriers during sequential unfolding that account for the observed nonexponentiality.

Orientation Dependence of DNA Blunt-End Stacking Studied by Free-Energy Simulations

DNA blunt ends can associate mediated by stacking interactions between the terminal base pairs that form blunt ends. The blunt end association plays a role in DNA repair and recombination processes and can also be of importance for the design of DNA-based nano-materials. Its function depends on the sequence and on the geometric arrangement that leads to stable interaction. For a stacked state, the relative orientation (twisting) of the base pairs is important. Molecular dynamics and advanced sampling simulations were used to calculate free energy change associated with twist changes of the stacked blunt-end base pairs. The calculations reproduce blunt stacking arrangements found in crystal structures of DNA oligonucleotides as free energy minima. To elucidate the physical origin of the stabilization of certain angular arrangements, the interactions between backbone atoms in the blunt-end stack were switched off in additional free energy calculations. It allows us to decipher the contributions to stacking stabilization due to the nucleobases and the backbone and to analyze the sequence dependence of the angular stacking preferences. Good qualitative agreement was also found for the comparison with quantum mechanical calculations. The results may help in the design of novel DNA-based materials.

A New Low-beta Regime for Unstable Proton Firehose Modes in Bi-kappa-distributed Plasmas

Abstract In the solar-wind plasma an excess of kinetic temperature along the background magnetic field stimulates proton firehose modes to grow if the parallel plasma beta parameter is sufficiently high, i.e., β p∥ ≳ 1. This instability can prevent the expansion-driven anisotropy from increasing indefinitely and explain the observations. Moreover, such kinetic instabilities are expected to be even more effective in the presence of suprathermal Kappa-distributed populations, which are ubiquitous in the solar wind and are less affected by collisions than the core population but contribute with an additional free energy. In this work we use both linear and extended quasi-linear (QL) frameworks to characterize the unstable periodic proton firehose modes (propagating parallel to the magnetic field) under the influence of suprathermal protons. Linear theory predicts a systematic stimulation of the instability, suprathermals amplifying the growth rates and decreasing the instability thresholds to lower anisotropies and lower plasma betas (β p∥ < 1). In perfect agreement with these results, the QL approach reveals a significant enhancement of the resulting electromagnetic fluctuations up to saturation with a stronger back reaction on protons, leading also to a faster and more efficient relaxation of the temperature anisotropy.

Determinants of conductance of a bacterial voltage-gated sodium channel

Through molecular dynamics (MD) and free energy simulations in electric fields, we examine the factors influencing conductance of bacterial voltage-gated sodium channel NavMs. The channel utilizes four glutamic acid residues in the selectivity filter (SF). Previously, we have shown, through constant pH and free energy calculations of pKa values, that fully deprotonated, singly protonated, and doubly protonated states are all feasible at physiological pH, depending on how many ions are bound in the SF. With 173 MD simulations of 450 or 500 ns and additional free energy simulations, we determine that the conductance is highest for the deprotonated state and decreases with each additional proton bound. We also determine that the pKa value of the four glutamic residues for the transition between deprotonated and singly protonated states is close to the physiological pH and that there is a small voltage dependence. The pKa value and conductance trends are in agreement with experimental work on bacterial Nav channels, which show a decrease in maximal conductance with lowering of pH, with pKa in the physiological range. We examine binding sites for Na+ in the SF, compare with previous work, and note a dependence on starting structures. We find that narrowing of the gate backbone to values lower than the crystal structure's backbone radius reduces the conductance, whereas increasing the gate radius further does not affect the conductance. Simulations with some amount of negatively charged lipids as opposed to purely neutral lipids increases the conductance, as do simulations at higher voltages.

Path Ensembles for Pin1-Catalyzed Cis-Trans Isomerization of a Substrate Calculated by Weighted Ensemble Simulations.

Pin1 enzyme protein recognizes specifically phosphorylated serine/threonine (pSer/pThr) and catalyzes the slow interconversion of the peptidyl-prolyl bond between cis and trans forms. Structural dynamics between the cis and trans forms are essential to reveal the underlying molecular mechanism of the catalysis. In this study, we apply the weighted ensemble (WE) simulation method to obtain comprehensive path ensembles for the Pin1-catalyzed isomerization process. Associated rate constants for both cis-to-trans and trans-to-cis isomerization are calculated to be submicroseconds time scales, which are in good agreement with the calculated free energy landscape where the cis form is slightly less favorable. The committor-like analysis indicates the shift of the transition state toward trans form (at the isomerization angle ω ∼ 110°) compared to the intrinsic position for the isolated substrate (ω ∼ 90°). The calculated structural ensemble clarifies a role of both the dual-histidine motif, His59/His157, and the basic residues, Lys63/Arg68/Arg69, to anchor both sides of the peptidyl-prolyl bond, the aromatic ring in Pro, and the phosphate in pSer, respectively. The rotation of the torsion angle is found to be facilitated by relaying the hydrogen-bond partner of the main-chain oxygen in pSer from Cys113 in the cis form to Arg68 in the trans form, through Ser154 at the transition state, which is really the cause of the shift in the transition state. The role of Ser154 as a driving force of the isomerization is confirmed by additional WE and free energy calculations for S154A mutant where the isomerization takes place slightly slower and the free energy barrier increases through the mutation. The present study shows the usefulness of the WE simulation for substantial path samplings between the reactant and product states, unraveling the molecular mechanism of the enzyme catalysis.

Free-energy transduction within autonomous systems.

The excess work required to drive a stochastic system out of thermodynamic equilibrium through a time-dependent external perturbation is directly related to the amount of entropy produced during the driving process, allowing excess work and entropy production to be used interchangeably to quantify dissipation. Given the common intuition of biological molecular machines as internally communicating work between components, it is tempting to extend this correspondence to the driving of one component of an autonomous system by another; however, no such relation between the internal excess work and entropy production exists. Here we introduce the "transduced additional free-energy rate" between strongly coupled subsystems of an autonomous system, which is analogous to the excess power in systems driven by an external control parameter that receives no feedback from the system. We prove that this is a relevant measure of dissipation-in that it equals the steady-state entropy production rate due to the downstream subsystem-and demonstrate its advantages with a simple model system.

Identification of Gating Sensitive Residues in TREK-2

TREK-2, a two-pore domain potassium (K2P) channel, is known to respond to a wide range of stimuli, such as pH, membrane tension, and binding of small ligands. Moreover, an “up” and a “down” x-ray crystallographic states have been resolved and it has been shown that the “up” state has higher ion conductance. However, molecular explanations for gating mechanisms and whether transitions between these two states play an important role in gating remain elusive. We initiate the study by free energy calculations with mutants of TREK-2 to predict how the conformational equilibrium between the “up” and the “down” states is shifted by mutations at the distal TM4 segment. We identify several mutants that exhibit a considerable shift towards the “up” state. Furthermore, additional free energy calculations suggest that the conformational shift is critically determined by the extent of steric clashes between two of the lower bundle helices. These findings shed light on the molecular roles of the identified gating sensitive residues in governing transitions between the two states, which potentially serve as a gating mechanism of TREK-1 and TREK-2 under different physiological conditions.

Distinct Tetracyanoquinodimethane Derivatives: Enhanced Fluorescence in Solutions and Unprecedented Cation Recognition in the Solid State.

Tetracyanoquinodimethane (TCNQ) is known to react with various amines to generate substituted TCNQ derivatives with remarkable optical and nonlinear optical characteristics. The choice of amine plays a crucial role in the outcome of molecular material attributes. Especially, mono/di-substituted TCNQ’s possessing strong fluorescence in solutions than solids are deficient. Furthermore, cation recognition in the solid-state TCNQ derivatives is yet undetermined. In this article, we present solution-enhanced fluorescence and exclusive solid-state recognition of K+ ion achieved through the selection of 4-(4-aminophenyl)morpholin-3-one (APM) having considerable π-conjugation and carbonyl (C=O) functionality, particularly in the ring. TCNQ when reacted with APM, in a single-step reaction, resulted in two well-defined distinct compounds, namely, 7,7-bis(4-(4-aminophenyl)morpholin-3-ono)dicyanoquinodimethane (BAPMDQ [1], yellow) and 7,7,8-(4-(4-aminophenyl)morpholin-3-ono)tricyanoquinodimethane (APMTQ [2], red), with increased fluorescence intensity in solutions than their solids. Crystal structure investigation revealed extensive C–H−π interactions and strong H-bonding in [1], whereas moderate to weak interactions in [2]. Surprisingly, simple mechanical grinding during KBr pellet preparation with [1, 2] triggered unidentified cation recognition with a profound color change (in ∼1 min) detected by the naked eye, accompanied by a drastic enhancement of fluorescence, proposed due to the presence of carbonyl functionality, noncovalent intermolecular interactions, and molecular assemblies in [1, 2] solids. Cation recognition was also noted with various other salts as well (KCl, KI, KSCN, NH4Cl, NH4Br, etc.). Currently, the recognition mechanism of K+ ion in [1, 2] is demonstrated by the strong electrostatic interaction of K+ ion with CO and simultaneously cation−π interaction of K+ with the phenyl ring of APM, supported by experimental and computational studies. Computational analysis also revealed that a strong cation−π interaction occurred between the K+ ion and the phenyl ring (APM) in [2] than in [1] (ΔGbinding calculated as ∼16.3 and ∼25.2 kcal mol–1 for [1] and [2], respectively) providing additional binding free energy. Thus, both electrostatic and cation−π interactions lead to the recognition. Scanning electron microscopy of drop-cast films showed microcrystalline “roses” in [1] and micro/nano “aggregates” in [2]. Optical band gap (∼3.565 eV) indicated [1, 2] as wide-band-gap materials. The current study demonstrates fascinating novel products obtained by single-pot reaction, resulting in contrasting optical properties in solutions and experiencing cation recognition capability exclusively in the solid state.