Flavor is considered one of the most significant factors affecting food quality. However, it is often susceptible to environmental factors, so encapsulation is highly necessary to facilitate proper handling and processing. In this study, the structural changes in starch encapsulation and their effects on flavor retention were investigated using indica starch (RS) as a matrix to encapsulate three flavoring compounds, namely nonanoic acid, 1-octanol, and 2-pentylfuran. The rheological and textural results suggested that the inclusion of flavor compounds improved the intermolecular interactions between starch molecules, resulting in a significant increase in the physicochemical properties of starch gels in the order: nonanoic acid > 1-octanol > 2-pentylfuran. The XRD results confirmed the successful preparation of v-starch. Additionally, the inclusion complexes (ICs) were characterized using FT-IR, SEM, and DSC techniques. The results showed that v-starch formed complexes with Flavor molecules. The higher enthalpy of the complexes suggested that the addition of alcohols and acids could improve the intermolecular complexation between starch molecules. The retention rates of three flavor compounds in starch were determined using HS-GC, with the values of 51.7 %, 32.37 %, and 35.62 %. Overall, this study provides insights into novel approaches to enhance the quality and flavor retention, improve the storability and stability, reduce losses during processing and storage, and extend the shelf life of starchy products.

The non-uniform distribution of colloidal particles in perovskite precursor results in an imbalanced response to the shear force during flexible printing process. Herein, it is observed that the continuous disordered migration occurring in perovskite inks significantly contributes to the enlargement of colloidal particles size and diminishes the crystallization activity of the inks. Therefore, a molecular encapsulation architecture by glycerol monostearate to mitigate colloidal particles collisions in the precursor ink, while simultaneously homogenizing the size distribution of perovskite colloids to minimize their diffusion disparities, is devised. The utilization of colloidal particles with a molecular encapsulation structure enables the achievement of uniform deposition during the printing process, thereby effectively balancing the crystallization rate and phase transition in the film and facilitating homogeneous crystallization of perovskite films. The large-area flexible perovskite device (1.01 cm2 and 100 cm2) fabricated through printing processes, achieves an efficiency of 24.45% and 15.87%, respectively, and manifests superior environmental stability, maintaining an initial efficiency of 91% after being stored in atmospheric ambiences for 150 days (unencapsulated). This work demonstrates that the dynamic evolution process of colloidal particles in both the precursor ink and printing process represents a crucial stride toward achieving uniform crystallization of perovskite films.

Olmesartan medoxomil (OLM) is a selective angiotensin II receptor antagonist used in the treatment of hypertension. Its therapeutic potential is limited by its poor water solubility, leading to poor bioavailability. Encapsulation of the drug substance by two methylated cyclodextrins, namely randomly methylated β-cyclodextrin (RM-β-CD) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TM-β-CD), was carried out to overcome the limitation related to OLM solubility, which, in turn, is expected to result in an improved biopharmaceutical profile. Supramolecular entities were evaluated by means of thermoanalytical techniques (TG-thermogravimetry; DTG-derivative thermogravimetry), spectroscopic methods including powder X-ray diffractometry (PXRD), universal-attenuated total reflectance Fourier-transform infrared (UATR-FTIR) and UV spectroscopy, saturation solubility studies, and by a theoretical approach using molecular modeling. The phase solubility method reveals an AL-type diagram for both inclusion complexes, indicating a stoichiometry ratio of 1:1. The values of the apparent stability constant indicate the higher stability of the host-guest system OLM/RM-β-CD. The physicochemical properties of the binary systems are different from those of the parent compounds, emphasizing the formation of inclusion complexes between the drug and CDs when the kneading method was used. The molecular encapsulation of OLM in RM-β-CD led to an increase in drug solubility, thus the supramolecular adduct can be the subject of further research to design a new pharmaceutical formulation containing OLM, with improved bioavailability.

We report a sensitive method for comparing weak interactions between aryl rings located on the external surfaces of equilibrating homo- and heterodimeric capsules. Two identical self-complementary resorcin[4]arene tetrabenzoate molecules and one tetramethylammonium cation form in CDCl3 hydrogen-bonded homodimeric capsules whose exteriors are decorated with four tight pairs of weakly interacting aryl rings. The pair wise mixing of six different homodimers establishes their equilibria with the corresponding heterodimeric species in which two types of aryl rings exert on each other some gentle forces. This equilibrium is significantly shifted either towards homo- or heterodimers depending on the nature and location of the substituents in the weakly interacting aryl rings. The thermodynamic favorability or disadvantage of the heterodimerization is determined by stronger or weaker aryl-aryl attractions in the hetero- or homodimeric capsules, respectively. The four-fold amplification of weak aryl-aryl interactions on the external surfaces of the equilibrating capsules is responsible for high sensitiveness of our approach.

Luminescent stability is a vital factor that dictates the application of lanthanide luminescent materials. Designing luminescent lanthanide cluster nodes that form an extended framework with predictable linking patterns may help enhance the structural stability of the lanthanide complexes and hence lead to improved luminescent stability. Herein, we report a series of one-dimensional (1D) rare-earth metal-organic framework compounds, {Ln4(μ4-OH)(TC4A)2(H2O)2(CH3O)(HCOO)2(HCOOH)}·xCH3OH (Ln = Sm (1), Eu (2), Tb (3), Dy (4); x = 1-5), based on double thiacalix[4]arene-capped Ln4(μ4-OH)(TC4A)2 nodes. The axially capped Ln4(μ4-OH)(TC4A)2 nodes are connected equatorially by formate bridges to form zigzag 1D-metal-organic framework (MOF) chains, which further assemble into a quasi-two-dimensional (2D) structure via hydrogen bonding. These unique features result in a stable structure and therefore superior luminescent stability. For example, the Tb-based 1D-MOF (3) exhibits intensive green photoluminescence with a quantum yield of 53% and an average decay time of 1.33 × 106 ns. It maintains its integrated emission intensity at 96.5, 94.5, and 89.4% of the original value after being exposed to moisture (soaking in water for 10 days), elevated temperature (150 °C), and UV (15 days of continuous radiation), respectively, demonstrating excellent luminescent stability. We adopt the Tb-based 1D-MOF (3) as the green phosphor and successfully fabricate a prototype white-light-emitting diode (LED) with stable emission under long-term operation. Our synthetic strategy allows control over the linking pattern of lanthanide nodes, providing a predictive route to obtain lanthanide MOFs with improved luminescent stability.

Two limiting cases of molecular recognition, induced fit (IF) and conformational selection (CS), play a central role in allosteric regulation of natural systems. The IF paradigm states that a substrate \"instructs\" the host to change its shape after complexation, while CS asserts that a guest \"selects\" the optimal fit from an ensemble of preexisting host conformations. With no studies that quantitatively address the interplay of two limiting pathways in abiotic systems, we herein and for the first time describe the way by which twisted capsule M-1, encompassing two conformers M-1(+) and M-1(-), trap CX4 (X=Cl, Br) to give CX4 ⊂M-1(+) and CX4 ⊂M-1(-), with all four states being in thermal equilibrium. With the assistance of 2D EXSY, we found that CBr4 would, at its lower concentrations, bind M-1 via a M-1(+)→M-1(-)→CBr4 ⊂M-1(-) pathway corresponding to conformational selection. For M-1 complexing CCl4 though, data from 2D EXSY measurements and 1D NMR line-shape analysis suggested that lower CCl4 concentrations would favor CS while the IF pathway prevailed at higher proportions of the guest. Since CS and IF are not mutually exclusive, we reason that our work sets the stage for characterizing the dynamics of a wide range of already existing hosts to broaden our fundamental understanding of their action. The objective is to master the way in which encapsulation takes place for designing novel and allosteric sequestering agents, catalysts and chemosensors akin to those found in nature.

By combining large-scale dissipative particle dynamics and steered molecular dynamics simulations, we investigate the mechanochemical cellular internalization pathways of homogeneous and heterogeneous nanohydrogels and demonstrate that membrane internalization is determined by the crosslink density and encapsulation ability of nanohydrogels. The homogeneous nanohydrogels with a high crosslink density and low encapsulation ability behave as soft nanoparticles partially wrapped by the membrane, while those with a low crosslink density and high encapsulation ability permeate into the membrane. Regardless of the crosslink density, the homogeneous nanohydrogels undergo typical dual morphological deformations. The local lipid nanodomains are identified at the contacting region between the membrane and nanohydrogels because of different diffusion behaviors between lipid and receptor molecules during the internalization process. The yolk@shell heterogeneous nanohydrogels present a different mechanochemical cellular internalization pathway. The yolk with strong affinity is directly in contact with the membrane, resulting in partial membrane wrapping, and the contacting area is much reduced when compared to homogenous nanohydrogels, leading to a smaller lipid nanodomain and thus avoiding related cellular toxicity. Our findings provide a critical mechanism understanding of the biological pathways of nanohydrogels and may guide the molecular design of the hydrogel-based materials for controlled release drug delivery, tissue engineering, and cell culture.

Risperidone (RSP) is an atypical antipsychotic drug which acts as a potent antagonist of serotonin-2 (5TH2) and dopamine-2 (D2) receptors in the brain; it is used to treat schizophrenia, behavioral and psychological symptoms of dementia and irritability associated with autism. It is a poorly water soluble benzoxazole derivative with high lipophilicity. Supramolecular adducts between drug substance and two methylated β-cyclodextrins, namely heptakis(2,6-di-O-methyl)-β-cyclodextrin (DM-β-CD) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TM-β-CD) were obtained in order to enhance RSP solubility and improve its biopharmaceutical profile. The inclusion complexes were evaluated by means of thermoanalytical methods (TG-thermogravimetry/DTG-derivative thermogravimetry/HF-heat flow), powder X-ray diffractometry (PXRD), universal-attenuated total reflectance Fourier transform infrared (UATR-FTIR), UV spectroscopy and saturation solubility studies. Job\'s method was employed for the determination of the stoichiometry of the inclusion complexes, which was found to be 2:1 for both guest-host systems. Molecular modeling studies were carried out for an in-depth characterization of the interaction between drug substance and cyclodextrins (CDs). The physicochemical properties of the supramolecular systems differ from those of RSP, demonstrating the inclusion complex formation between drug and CDs. The RSP solubility was enhanced as a result of drug encapsulation in the CDs cavity, the higher increase being obtained with DM-β-CD as host; the guest-host system RSP/DM-β-CD can thus be a starting point for further research in developing new formulations containing RSP, with enhanced bioavailability.

Design, synthesis, and applications of metal-organic frameworks (MOFs) are among the most salient fields of research in modern inorganic and materials chemistry. As the structure and physical properties of MOFs are mostly dependent on the organic linkers or ligands, the choice of ligand system is of utmost importance in the design of MOFs. One such crucial organic linker/ligand is terpyridine (tpy), which can adopt various coordination modes to generate an enormous number of metal-organic frameworks. These frameworks generally carry physicochemical characteristics induced by the π-electron-rich (basically N-electron-rich moiety) terpyridines. In this minireview, the construction of 3D MOFs associated with symmetrical terpyridines is discussed. These ligands can be easily derivatized at the lateral phenyl (4\'-phenyl) position and incorporate additional organic functionalities. These functionalities lead to some different binding modes and form higher dimensional (3D) frameworks. Therefore, these 3D MOFs can carry multiple features along with the characteristics of terpyridines. Some properties of these MOFs, like photophysical, chemical selectivity, photocatalytic degradation, proton conductivity, and magnetism, etc. have also been discussed and correlated with their frameworks.

Covalent capsule 1 was designed to include two molecular baskets linked with three mobile pyridines tucked into its inner space. On the basis of both theory (DFT) and experiments (NMR and X-ray crystallography), we found that the pyridine \"doors\" split the chamber (380 Å3 ) of 1 so that two equally sizeable compartments (190 Å3 ) became joined through a conformationally flexible aromatic barrier. The compartments of such unique host could be populated with CCl4 (88 Å3 ; PC=46 %), CBr4 (106 Å3 ; 56 %) or their combination CCl4 /CBr4 (PC=51 %), with thermodynamic stabilities ΔG° tracking the values of packing coefficients (PC). Halogen (C-X⋅⋅⋅π) and hydrogen bonding (C-H⋅⋅⋅X) contacts held the haloalkane guests in the cavities of 1. The consecutive complexations were found to occur in a negative allosteric manner, which we propose to result from the induced-fit mode of complexation. Newly designed 1 opens a way for probing the effects of inner conformational dynamics on noncovalent interactions, reactivity and intramolecular translation in confined spaces of hollow molecules.