Stable Molecules Research Articles

Spontaneous Generation of -CH2CN from Acetonitrile at the Air-Water Interface.

Acetonitrile (CH3CN) is considered a very stable molecule in aqueous solutions, and its deprotonation to produce strongly basic -CH2CN requires harsh conditions. CH3CN is also present in the atmosphere, but its chemical transformation pathway at the air-water interface is unknown. In this study, we discovered and verified the unprecedented spontaneous generation of -CH2CN from the CH3CN-H2O solution at the air-water interface of microdroplets, and revealed the indirect deprotonation mechanism of CH3CN by synergistic redox of •OH and electrons in the microdroplets through the capture of key intermediates and computational chemistry. In addition, the dynamic process of indirect deprotonation-protonation was also observed. The high reactivity of -CH2CN in the droplets was revealed via nucleophilic addition to acetone, benzaldehyde, and the parent CH3CN molecule. Furthermore, the -CH2CN generated in the microdroplets underwent a barrier-free nucleophilic addition reaction with CO2 to produce 2-cyanoacetic acid for CO2 fixation. The synergistic redox reaction process revealed in this study provides new insights into microdroplet chemistry, and the distinctive CH3CN reactions identified may provide new clues to unravel the mystery of the CH3CN transformation in the atmospheric environment.

Pattern formations and their active manipulation in a Rydberg noisy-dressed Bose-Einstein condensate.

We investigate the formation and manipulation of spatial patterns and their structural phase transitions by examining the effects of laser linewidth on the dynamics of Rydberg noise-dressed Bose-Einstein condensates (RnD BECs). We discover that the homogeneous matter wave can transition into various types of self-organized patterns, which are manipulated by tuning the laser linewidth, control field intensity, and atomic density. Remarkably, the system exhibits stable nonlocal matter-wave solitons, vortices, and soliton molecules under specific laser linewidths.

AuAg plasmonic nanoalloys with asymmetric charge distribution on CeO2 nanorods for selective photocatalytic CO2‐to‐CH4 conversion

AbstractConverting CO2 under mild conditions by employing semiconductor photocatalysts is promising to address global environmental issues. However, the current CO2 conversion efficiency is limited by the difficulty activating the thermodynamically stable CO2 molecules. Constructing plasmonic nanoalloy‐based photocatalytic systems with significant localized surface plasmon resonance (LSPR) is full of potential but remains a vast challenge. In this work, AuAg plasmonic nanoalloys were incorporated on CeO2 nanorods (designated as AuAg–CeO2) to achieve selective photoreduction of CO2. The result displays that Ag can serve as a superior electron modifier to promote the electron enrichment of Au, thus producing asymmetric charge distributions to boost the selective conversion of CO2. Furthermore, the improved LSPR effect on AuAg–CeO2 induces the generation of high‐energy hot electrons under irradiation, enhancing the reactivity of electrons for CO2 photoreduction. Due to the aforementioned effects, AuAg–CeO2 exhibits a high CO2‐to‐CH4 performance of 92.6 μmol g−1 through a 3‐h test and a high CH4 selectivity of 94.5%, up to 2.6, 8.7, and 17.1 times higher than the activity of Au–CeO2, pure CeO2, and Ag–CeO2, respectively. This work can provide a new perspective for constructing high‐performance catalysts for photocatalytic CO2 reduction.

In Situ Molecular Reconfiguration of Pyrene Redox-Active Molecules for High-Performance Aqueous Organic Flow Batteries.

Aqueous organic flow batteries (AOFBs) hold great potential for large-scale energy storage, however, scalable, green, and economical synthetic methods for stable organic redox-active molecules (ORAMs) are still required for their practical applications. Herein, pyrene-based ORAMs are obtained via an in situ organic electrolysis strategy in a flow cell. It is revealed that the water attacking pyrenes restructured molecules to produce a variety of isomers and dimers during the electrolysis, which can be modulated by regulating the local electron cloud density and steric hindrance of pyrene precursors. As a result, the molecularly reconfigured pyrene-based catholytes, even without any further purification, achieved a high electrolyte utilization of ≈96% and volumetric capacity above 50AhL-1. Inspiringly, remarkable cell stability with almost no capacity decay for ≈70 days is achieved, benefiting from the robust aromatic structure of the pyrene cores. The insights into the in situ electrosynthesis of pyrene-based ORAMs provided in the work will provide guidance for designing ultra-stable ORAMs for AOFB applications.

Broadband Rotational Spectroscopy in Uniform Supersonic Flows: Chirped Pulse/Uniform Flow for Reaction Dynamics and Low Temperature Kinetics.

ConspectusThe study of gas-phase chemical reactions at very low temperatures first became possible with the development and implementation of the CRESU (French acronym for Reaction Kinetics in Uniform Supersonic Flows) technique. CRESU relies on a uniform supersonic flow produced by expansion of a gas through a Laval (convergent-divergent) nozzle to produce a wall-less reactor at temperatures from 10 to 200 K and densities of 1016-1018 cm-3 for the study of low temperature kinetics, with particular application to astrochemistry. In recent years, we have combined uniform flows with revolutionary advances in broadband rotational spectroscopy to yield an instrument that affords near-universal detection for novel applications in photodissociation, reaction dynamics, and kinetics. This combination of uniform supersonic flows with chirped-pulse Fourier-transform microwave spectroscopy (Chirped-Pulse/Uniform Flow, CPUF) permits detection of any species with a modest dipole moment, thermalized to the uniform temperature of the gas flow, with isomer, conformer, and vibrational state specificity. In addition, the use of broadband, high-resolution, and time-dependent (microsecond time scale) micro- and mm-wave spectroscopy makes it an ideal tool for characterizing both transient and stable molecules, as well as studying their spectroscopy and dynamics.In this Account, we review recent advances made using the CPUF technique, including studies of photodissociation, radical-radical reaction dynamics, and low temperature kinetics. These studies highlight both the strength of universal and multiplexed detection and the challenges of coupling it to a high-density collisional environment. Product branching and product evolution as a function of time have been measured for astrochemically relevant systems, relying on the detailed characterization of these flow conditions via experiments and fluid dynamics simulations. In the photodissociation of isoxazole, an unusual heterocyclic molecule with a very low-energy conical intersection, we have identified 7 products in 5 reaction channels and determined the product branching, pointing to both direct and indirect pathways. We have also approached the same system from separated NO and C3H3 reactants to explore a broader range of the potential energy surface, demonstrating the power of multichannel branching measurements for complex radical-radical reactions. We determined the product branching in the C3H2 isomers in the photodissociation of the propargyl radical and identified the importance of a hydrogen atom catalyzed isomerization to the lowest energy cyclic form. This then motivated a study of direct D-H exchange reaction in radicals, in which we demonstrate that it is an important and overlooked pathway for deuterium fractionation in astrochemical environments. Recently, we have shown the measurement of low temperature kinetics inside an extended Laval nozzle, after which a shock-free secondary expansion to low temperature and density affords an ideal environment for detection by rotational spectroscopy. These results highlight the power and potential of the CPUF approach, and future prospects will also be discussed in light of these developments.

Milestones in the Technology of Modified Starch in Pharmaceutical Formulation

Abstract: Carbohydrates, the most prevalent class of organic substances in living systems, play a variety of important roles, such as in the creation of energy, the construction of biological structures, and the synthesis of paper and food. More advanced uses of modified starch have been introduced over the past millennium, demonstrating that modified starches are promising excipients in drug delivery, an area in which their role and range of utility continuously increase. Technological advancements in the pharmaceutical field have led to the development of new and highly stable molecules with enhanced properties for novel drug delivery systems. Innovative starches from various sources present exclusive support in the development of novel dosage forms.

Response Matching for Generating Materials and Molecules.

Diffusion models have recently emerged as powerful tools for the generation of new molecular and material structures. The key insight is that the noise in these models is related to the response of the atoms to displacement, and the denoising step is thus analogous to the geometry relaxation of atomistic systems starting from a random structure. Building on this, we present a generative method called Response Matching (RM), which leverages the fact that each stable material or molecule exists at the minimum of its potential energy surface. Any perturbation induces a response in energy and stress, driving the structure back to equilibrium. Matching this response is closely related to score matching in diffusion models. Another important aspect of state-of-the-art diffusion models is the incorporation of physical symmetries such as translation, rotation, and periodicity. RM employs a machine learning interatomic potential and random structure search as the denoising model, inherently respecting these symmetries and exploiting the locality of atomic interactions. RM handles both molecules and bulk materials under the same framework. Its efficiency and generalization are demonstrated on three systems: a small organic molecular data set, stable crystals from the Materials Project, and one-shot learning on a single diamond configuration.

Catalytic degradation of stable benzene molecules under room temperature conditions over Pt-loaded boron-carbon-nitride (Pt/BCN) catalysts

The catalytic degradation of volatile organic compounds (VOCs) such as benzene via ring-opening at room temperature is challenging due to the presence of π-bonds in the ring-forming carbon atoms. This study involved the preparation of a novel Pt-loaded boron-carbon-nitride (Pt/BCN) catalyst containing single-atom active sites for efficient catalysis of benzene degradation at room temperature in air. The micromorphology, surface structure, and coordination environment of the catalyst were analyzed using characterization techniques including aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC–HAADF–STEM) and X-ray absorption fine structure (XAFS). The degradation mechanism was investigated using electron paramagnetic resonance (EPR) and in situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS). The experimental results demonstrate that Pt/BCN contains many Pt-N4 single-atom active sites that can generate hydroxyl radicals under room-temperature air conditions, leading to the oxidation of benzene to CO2 and H2O. Containing atomically dispersed active-site catalysts developed in this study offer a theoretical foundation for designing catalyst active centers in related fields and advancing the industrial application of room-temperature, low-carbon VOCs treatment technologies.

Predicting pKa Values of Para-Substituted Aniline Radical Cations vs. Stable Anilinium Ions in Aqueous Media

The focus of pKa calculations has primarily been on stable molecules, with limited studies comparing radical cations and stable cations. In this study, we comprehensively investigate models with implicit solvent and explicit water molecules, direct and indirect calculation approaches, as well as methods for calculating free energy, solvation energy, and quasi-harmonic oscillator approximation for para-substituted aniline radical cations (R-PhNH2•+) and anilinium cations (R-PhNH3+) in the aqueous phase. Properly including and positioning explicit H2O molecules in the models is important for reliable pKa predictions. For R-PhNH2•+, precise pKa values were obtained using models with one or two explicit H2O molecules, resulting in a root mean square error (RMSE) of 0.563 and 0.384, respectively, for both the CBS-QB3 and M062X(D3)/ma-def2QZVP methods. Further improvement was achieved by adding H2O near oxygen-containing substituents, leading to the lowest RMSE of 0.310. Predicting pKa values for R-PhNH3+ was more challenging. CBS-QB3 provided an RMSE of 0.349 and the M062X(D3)/ma-def2QZVP method failed to calculate pKa accurately (RMSE > 1). However, by adopting the double-hybrid functional method and adding H2O near the R substituent group, the calculations were significantly improved with an average absolute difference (ΔpKa) of 0.357 between the calculated and experimental pKa values. Our study offers efficient and reliable methods for pKa calculations of R-PhNH2•+ (especially) and R-PhNH3+ based on currently mature quantum chemistry software.

Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza-Hetero Aromatic Compounds.

Excited states of radical anions derived from the photoreduction of stable organic molecules are suggested to serve as potent reductants. However, excited states of these species are too short-lived to allow bimolecular quenching processes. Recently, the singlet excited state of Meisenheimer complexes, which possess a long-lived excited state, was identified as the competent species for the reduction of challenging organic substrates (-2.63 V vs. SCE, saturated calomel electrode). To produce reasonably stable and simply accessible different Meisenheimer complexes, the addition of nBuLi to readily available aromatic heterocycles was investigated, and the photoreactivity of the generated species was studied. In this paper, we present the straightforward preparation of a family of powerful photoreductants (*Eox<-3 V vs. SCE in their excited states, determined by DFT and time-dependent TD-DFT calculations; DFT, density functional theory) that can induce dehalogenation of electron-rich aryl chlorides and to form C-C bond through radical cyclization. Photophysical analyses and computational studies in combination with experimental mechanistic investigations demonstrate the ability of the adduct to act as a strong electron donor under visible light irradiation.

Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Hetero Aromatic Compounds

AbstractExcited states of radical anions derived from the photoreduction of stable organic molecules are suggested to serve as potent reductants. However, excited states of these species are too short‐lived to allow bimolecular quenching processes. Recently, the singlet excited state of Meisenheimer complexes, which possess a long‐lived excited state, was identified as the competent species for the reduction of challenging organic substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably stable and simply accessible different Meisenheimer complexes, the addition of nBuLi to readily available aromatic heterocycles was investigated, and the photoreactivity of the generated species was studied. In this paper, we present the straightforward preparation of a family of powerful photoreductants (*Eox&lt;−3 V vs. SCE in their excited states, determined by DFT and time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation of electron‐rich aryl chlorides and to form C−C bond through radical cyclization. Photophysical analyses and computational studies in combination with experimental mechanistic investigations demonstrate the ability of the adduct to act as a strong electron donor under visible light irradiation.

Harmonizing Between Chemical Functionality and Surface Area of Porous Organic Polymeric Nanotraps for Tuning Carbon Dioxide Capture.

The energy sector has demonstrated significant enthusiasm for investigating post-combustion CO2 capture, storage, and separation. However, the practical application of current porous adsorbents is impeded by challenges related to cost competitiveness, stability, and scalability. Intregation of heteroatoms in the porous organic polymers (POPs) dispense it more susceptible for CO2 adsorption to attenuate green house gases. In this regard, two hydroxy rich hypercrosslinked POPs, namely Ph/Tt-POP have been developed by one-pot condensation polymerization using a facile synthetic strategy. The high surface areas of both the Ph/Tt-POP (1057 and 893 m2g-1, respectively), and the heteroatom functionality in the POP framework instigated us to explore our material for CO2 adsorption study. The CO2 uptake capacities in Ph/Tt-POP are found to be 2.45 and 2.2 mmol g-1, at 273 K respectively. Further, in-situ static 13C NMR experiment shows that CO2 molecules in Tt-POP appear to be less mobile than those in Ph-POP which probably due to the presence of triazine functional groups along with high abundant -OH groups in the Tt-POP framework. An in-depth study of the CO2 adsorption mechanism by density functional theory (DFT) calculations also shows that CO2 adsorption at the cages formed by two benzyl rings represents the most stable interaction and CO2 molecule is more favorably adsorbed on the Ph-POP with the more negative interaction energies values compared to that of Tt-POP. Further, Non-covalent interaction (NCI) plot reveals that CO2 molecules adsorb more on the Ph-POP than Tt-POP, which can be explain by hydrogen bond formation in case of Tt-POP repeating units turning aside CO2 molecule to interact with the Ph component. Overall, our present study reflects the comprising effects of surface area of the solid adsorbents as well as their functionality can be beneficial for developing efficient hypercrosslinked porous polymers as solid CO2 adsorbent.

Substrate interactions guide cyclase engineering and lasso peptide diversification.

Lasso peptides are a diverse class of naturally occurring, highly stable molecules kinetically trapped in a distinctive [1]rotaxane conformation. How the ATP-dependent lasso cyclase constrains a relatively unstructured substrate peptide into a low entropy product has remained a mystery owing to poor enzyme stability and activity in vitro. In this study, we combined substrate tolerance data with structural predictions, bioinformatic analysis, molecular dynamics simulations and mutational scanning to construct a model for the three-dimensional orientation of the substrate peptide in the lasso cyclase active site. Predicted peptide cyclase molecular contacts were validated by rationally engineering multiple, phylogenetically diverse lasso cyclases to accept substrates rejected by the wild-type enzymes. Finally, we demonstrate the utility of lasso cyclase engineering by robustly producing previously inaccessible variants that tightly bind to integrin αvβ8, which is a primary activator of transforming growth factor β and, thus, an important anti-cancer target.

The Impact of Polychlorinated Biphenyls on the Development of Zebrafish (Danio rerio).

Polychlorinated biphenyls (PCBs) are a group of 209 highly stable molecules that were used extensively in industry. Although their commercial use ceased in 1979, they are still present in many aquatic ecosystems due to improper disposal, oceanic currents, atmospheric deposition, and hydrophobic nature. PCBs pose a significant and ongoing threat to the development and sustainability of aquatic organisms. In areas with PCB exposure high mortality rates of organisms inhabiting them are still seen today, posing a significant threat to local species. Zebrafish were exposed to a standard PCB mixture (Aroclor 1254) for the first 5 days post fertilization, as there is a gap in knowledge during this important developmental period for fish (i.e., organization of the body). This PCB mixture was formally available commercially and has a high prevalence in PCB-contaminated sites. We tested for the effects of PCB dosage (control (embryo water only; 0 mg/L), methanol (solvent control; 0 mg/L); PCB 1 (0.125 mg/L), PCB 2 (0.25 mg/L), PCB 3 (0.35 mg/L), and PCB 4 (0.40 mg/L)) on zebrafish survival, rate of metamorphosis, feeding efficiency, and growth. We found significant, dose-dependent effects of PCB exposure on mortality, feeding efficiency, and growth, but no clear effect of PCBs on the rate of zebrafish metamorphosis. We identified a concentration in which there were no observable effects (NOEC), PCB concentration above the NOEC had a significant impact on life-critical processes. This can further inform local management decisions in environments experiencing PCB contamination.

Hexa-Penta nanobelt: a novel stable structure with potential optical application

ABSTRACT We report a theoretical investigation of a new carbon nanobelt called Hexa-Penta-belt with molecular formula C 42 H 18 . Hexa-Penta-belt is a variation of the synthesised Methylene-bridged[6]cycloparaphenylene (M-b[6]CPP) with molecular formula C 42 H 24 . Hexa-Penta-belt consists of carbon pentagon and hexagon rings and was inspired by the Penta-belt (theoretically derived from the penta-graphene sheet), the [12]cyclophenacene, and the M-b[6]CPP synthesised by Itami and Segawa [1]. Using Density Functional Theory (DFT), we calculated Hexa-Penta-belt electronic, optical, and thermodynamic properties and their vibrational frequencies. Hexa-Penta-belt is a structurally and thermally stable molecule, as Quantum Molecular Dynamics (QMD) showed. The results exhibited that the Hexa-Penta-belt has excellent electronic stability comparable to C 60 , and it behaves as a semiconductor with a gap estimated at 0.89 eV. It absorbs in the ultraviolet and the visible region (corresponding to the violet, green, and red colours) presenting an absorption more consistent in the visible region than M-b[6]CPP, which could indicate application, for example, as an optical nanosensor. We verified through the carbon atom binding energy that Hexa-Penta-belt is an intermediate molecule between Penta-belt and [12]cyclophenacene.

Recent Advances in Synthesis and Applications of Calixarene Derivatives Endowed with Anticancer Activity.

Calix[n]arenes, macrocycles constituted of 4-8 phenol moieties linked through methylene bridges, are stable molecules that can be selectively functionalised at the upper or lower rim. It has already been demonstrated that calixarene derivatives can be biologically or pharmacologically active compounds. More recently, suitably functionalised calixarenes and calixarene analogues (dihomooxacalixarenes, thiacalixarenes, calix[4]resorcinols, azacalixarenes, calixpyrroles, and pillarenes) were found to act as anticancer agents, at least in in vitro assays. We are reporting on the latest progress in this research field.

Molecular-level insight into the effect of fertilization regimes on the chemodiversity of dissolved organic matter in tropical cropland

Fertilization is a critical agronomic measure for croplands in tropical regions, owing to their low fertility. However, the effects of fertilization on the quantity and chemodiversity of latosolic dissolved organic matter (DOM) in tropical regions remain largely unknown. Therefore, in this study, the variations in latosol DOM concentrations and chemodiversity induced by inorganic fertilization and the co-application of inorganic fertilization with straw return, sheep manure, biochar, and vermicompost fertilizers at a molecular level were systematically investigated using multispectral techniques and ultrahigh-resolution mass spectrometry. In line with our expectations, the results showed that combined inorganic-organic fertilization improved soil quality by increasing soil organic carbon content compared to that under inorganic fertilization. However, as the most active and bioavailable organic carbon pool, dissolved organic carbonconcentrations between the fertilization treatments were not significantly different (p = 0.07). However, the dissolved organic carbon concentrations under combined inorganic-organic fertilization treatment (NPK plus straw return, 263.45 ± 37.51 mg/kg) were lower than those under inorganic fertilization treatment (282.10 ± 18.57 mg/kg). Spectral analysis showed that the DOM in the combined inorganic-organic fertilization treatments had a higher degree of humification and lower autogenetic contributions. Furthermore, Fourier transform ion cyclotron resonance mass spectrometry analysis indicated that the combined inorganic-organic fertilization increased the chemodiversity of latosolic DOM and promoted the production of large, oxidized, and stable molecules, including lignin, aromatic, and tannin compounds, which potentially benefits soil carbon sequestration in tropical regions. This study could provide a theoretical basis for elucidating on the potentially relevant ecological functions and environmental effects of DOM under fertilization regimes.

Heavy-atom tunnelling in benzene isomers: how many tricyclic species are truly stable?

The variety of possible benzene isomers may provide a fundamental basis for understanding structural and reactivity patterns in organic chemistry. However, the vast majority of these isomers remain unsynthesized, while most of the experimentally known species are only moderately stable. Consequently, there is a high probability that the theoretically proposed isomers would also be barely metastable, a factor that must be taken into account if their creation in the laboratory is sought. In this work, we studied the kinetic stability of all 73 hypothetical tricyclic benzene isomers, especially focusing on their nuclear quantum effects. With this in mind, we evaluated which species are theoretically possible to synthesize, detect, and isolate. Our computations predict that 26% of the previously deemed stable molecules are completely unsynthesizable due to their intrinsic quantum tunnelling instability pushing for their unimolecular decomposition even close to the absolute zero. Five more systems would be detectable, but they will slowly and inevitably degrade, while seven more supposedly stable systems will break apart in barrierless mechanisms.

Towards Stable Helical Structures with Enhanced Molecular Conductance by Strengthening Through‐Space Conjugation

Developing long‐chain molecules with stable helical structures is of significant importance for understanding and modulating the properties and functions of helical biological macromolecules, but challenging. In this work, an effective and facile approach to stabilize folded helical structures by strengthening through‐space conjugation is proposed, using new ortho‐hexaphenylene (o‐HP) derivatives as models. The structure‐activity relationship between the through‐space conjugation and charge transport behavior of the prepared folded helical o‐HP derivatives is experimentally and theoretically investigated. It is demonstrated that the through‐space conjugation within o‐HP derivatives can be strengthened by introducing electron‐withdrawing pyridine and pyrazine, which can effectively stabilize the helical structures of o‐HP derivatives. Moreover, scanning tunneling microscopy‐break junction measurements reveal that the stable regular helical structures of o‐HP derivatives open up dominant through‐space charge transport pathways, and the single‐molecule conductance is enhanced by more than 70% by strengthening through‐space conjugation with pyridine and pyrazine. But the through‐bond charge transport pathways contribute much less to the conductance of o‐HP derivatives. These results not only provide a new method for exploring stable helical molecules, but also pave a stepping stone for deciphering and modulating the charge transport behavior of helical systems at the single‐molecule level.

All-optical organic photochemical integrated nanophotonic memory: low-loss, continuously tunable, non-volatile

Controlling changes in the optical properties of photonic devices allows photonic integrated circuits (PICs) to perform useful functions, leading to a large breadth of applications in communications, computing, and sensing. Many mechanisms to change optical properties exist, but few allow doing so in a reversible, non-volatile manner. Without such mechanisms, power inefficiencies and use of external memory are inevitable. In this work, we propose and experimentally demonstrate reversible, non-volatile phase actuation of a silicon nitride PIC with thermally stable photochromic organic molecules vapor-deposited within a slot waveguide structure. The use of a high-core-index platform allows the photochemical phase actuation of a planar-resonator-based photonic memory unit, which enables positive and negative signal weighting and permits integrated spectroscopic analysis. We show properties of this all-optical memory for a silicon photonics platform, including low loss in the optical C-band, first-order photokinetics of the photoconversion, bidirectional scalable switching, and continuous tuning. Such features are critical for memories in analog applications such as quantum, microwave, and neuromorphic photonics, where bipolar weights, low loss, and precision are paramount. More generally, this work suggests that back-end-of-line-compatible vapor deposition of organic molecules into silicon photonic circuits is promising to introduce non-silicon-native functionality.