Weak Intermolecular Interactions Research Articles

Adaptive structural modification of Zr-based MOF-808 via solvent and ligand engineering for enhanced fluoride ion adsorption efficiency

The rapid development of industries such as new energy and photovoltaic has led to the generation of a large amount of industrial fluorine wastewater, posing serious threats to water environment and human health. To address this issue, MOF-808 adsorbent was synthesized by controlling the synthesis conditions and modifying the ligand structure. Batch adsorption experiments were conducted by varying experimental conditions, including type of adsorbent, pH, wastewater concentration, adsorption time, temperature, and interfering anions. The adsorption behavior of MOF-808-AA towards fluoride ions was well fitted by the Elovich non-linear kinetic model, as well as the Freundlich and Temkin non-linear isotherm models, indicating that the adsorption behavior was influenced by multiple mechanisms other than just intraparticle diffusion. Thermodynamic results suggested a spontaneous exothermic monolayer chemical adsorption process. Under the conditions of pH 6.0 and T = 298 K, MOF-808-AA exhibited a maximum adsorption capacity of 84.65 mg/g for fluoride ions. Characterization techniques, as well as quantum chemical analysis was employed to analyze the adsorption behavior and predict the reaction sites. The potential mechanism can be summarized as the formation of new bonds between MOF-808-AA and the adsorbed fluoride ions, as well as the weak intermolecular interactions such as hydrogen bonding and vdW forces. Furthermore, MOF-808-AA demonstrated satisfactory reusability and excellent chemical stability during the cyclic process. These findings suggest the potential application of MOF-808-AA for removing fluoride ions from wastewater.

Effect of Fatty Acid Unsaturation on the Intermolecular Weak Interaction at the Low-Rank Coal-Water Interface: Density Functional Theory Calculations and Experimental Study.

The study on the effect of fatty acid saturation on low-rank coal (LRC) flotation is still limited. In this investigation, density functional theory (DFT) combined with Zeta potential and Fourier transform infrared spectroscopy (FTIR) was used to study the mechanism of intermolecular weak interaction at the LRC-water interface of fatty acids (decanoic acid (DA), undecylenic acid (UA), and phenyl propionic acid (PA)) with different saturations and different dodecane (D) composition hydrocarbon oil-fatty acid mixed collectors (D-DA, D-UA, D-PA). The findings demonstrated that the hydrogen bond interaction and electrostatic interaction between the UA/PA with unsaturated bonded carbon chains and the LRC molecular fragments/water molecules were stronger than DA without a saturated bond carbon chain, and UA/PA strengthened its interaction with water molecules on the whole, even PA molecules would preferentially interact with water molecules. The unsaturated bond had a minimal impact on the adsorption of the LRC hydrophobic site, and the strength of the hydrogen bond between the mixed collector and LRC is D-DA > D-UA > D-PA. In the actual flotation process, the strong hydrogen bonding and electrostatic interaction between UA/PA and water molecules weaken the collection performance of the mixed collector D-UA/D-PA for LRC, which also confirmed the research results of DFT, FTIR, and Zeta.

Study of the relationship between pressure and sensitivity of energetic materials based on first-principles calculation.

In order to study the relationship between the sensitivity and pressure of energetic materials, six kinds of energetic materials were selected as the research object. The crystal structure, electronic, and phonon properties under hydrostatic pressure of 0 ~ 45 GPa were calculated by first principles. The calculation results show that the lattice parameters and band gap values of these six energetic materials decrease with the increase of pressure. The peak of the density of states decreases and moves to the low energy direction, and the electrons become more active. Meanwhile, the effect of pressure on the sensitivity of the energetic materials is analyzed based on the multi-phonon up-pumping theory. The number of doorway modes and integral of projected phonon density of states under high pressure is calculated. The results show that both of them increase with the increase of pressure. And the smaller the value of the band gap, the larger the number of doorway modes and integral of projected phonon density of states, and the more sensitive the energetic material is. All calculations are performed using the Materials Studio software based on density functional theory. The Perdew-Burke-Ernzerhof (PBE) functional of the generalized gradient approximation (GGA) is used to calculate the exchange correlation function, and the Grimme dispersion correction method is used to deal with the weak intermolecular interaction. The structure of the compound was optimized by BFGS algorithm. The linear response is used to calculate the phonon properties of energetic materials. The plane wave cutoff energy was set to 830eV. The K-point grids of TATB, FOX-7, TNX, RDX, TNT, and HMX were chosen as 2 × 2 × 2, 2 × 2 × 1, 2 × 1 × 1, 1 × 1 × 1, 1 × 2 × 1, and 2 × 1 × 2.

A model of ionization-induced reactions in CH4/N2 clusters in Titan's atmosphere: theoretical insights into mono- and divalent states

Abstract We propose a model for ionization-induced reactions between N2 and CH4, the main components of Titan's atmosphere, and examine their mechanism using quantum mechanical and molecular dynamics methods. Bimolecular CH4–N2 clusters form through collision, and their conformation depends on the encounter cross section due to weak intermolecular interaction. These clusters acquire a driving force through vertical ionization because the vertically ionized structure is not situated at the minimum of the potential energy surface in the ionized state. This leads to multiple reactions, overcoming energy barriers in the process. In the divalent state, a robust attractive interaction occurs between CH4 and N2 through charge transfer. Subsequently, the H4C–N2 covalent bond forms prior to reactions, resulting in the production of N2H+, CH3+, CH3N2+, and CH2N2+; otherwise only N2H+, CH3+, and CH2+ are generated. In contrast, when ionized to a monovalent state, although dissociation of N2H+ and isomerization to CH3NHN+ and CH3NNH+ occurs, a significant portion dissociates into CH4+ and N2 without undergoing further reactions. Additionally, the generation of N2H+ and CH3+ is limited in the monovalent state, primarily due to a lower driving force and the absence of Coulombic explosion. Our computational results highlight the pivotal role of divalent reactions within Titan's atmosphere, which are more efficient than monovalent reactions.

Fluorescence Switching and Photoisomerization of a Spiropyran Molecular Photoswitch through Confined Spaces Regulation in Crystals.

Spiropyran (SP) and its derivatives are highly attractive owing to their distinctive merits in high contrast and fast response read-out systems. However, the realization of photoswitching properties of SP is hindered in the aggregate state, particularly in crystals owing to the dense packing of molecules leading to insufficient study of the relationship between the molecular structure/stacking mode and photoswitching behavior. Herein, we report three SP derivatives: different flexible chains (carboxyl group for SP-0 and ester group for SP-1) are attached to the indoline moiety, while the ester group is attached to the chromene moiety for SP-2. SP-1 exhibits fluorescent photoswitching properties in crystals due to the weak intermolecular interactions resulting in enough free space for the photoisomerization. The presence of hydrogen bonds in SP-0 enhances the molecular interactions to restrict the photoisomerization, and the ester group of SP-2 impacts the thermodynamic properties, thereby limiting the realization of photoswitching of SP-2.

Insight into the interaction between zirconium dibutyl phosphate complex and diluents: An experimental and computational study

In solvent extraction processes, there are challenges caused by the formation of the third phase or interfacial precipitation. The branched alkanes have been used as diluents to disrupt the third-phase formation, while there is little study about the effect of diluents on the appearance of precipitation. Here, we report the inhibiting effect of the novel hyperbranched alkane diluent (HAD) on the formation of zirconium-dibutyl phosphate (Zr-DBP) precipitation and investigate the formation mechanism by the density functional theory (DFT) theory. The extraction experiments show that HAD as the diluent has a remarkable inhibiting ability to form Zr-DBP precipitation, compared with n-dodecane and kerosene. The spectra show no noticeable difference in the composition and structures of the precipitations formed in the three diluents. The energetics from the DFT calculations suggest the P-OH and P=O ligands on one HDBP molecule can bridge two Zr-DBP complexes into a dimer and then aggregate into the precipitation. Besides, the interactions between diluent-diluent molecules play a significant role in precipitation formation. The straight-chain n-dodecanes have a strong intermolecular dispersion force and tend to attract each other but not the Zr-DBP complex. However, the branched alkanes with weak intermolecular interactions have a better dispersive capacity for Zr-DBP complexes, due to the much higher dispersion force of diluent-complex interaction than that of the diluent-diluent interaction. This work provides a new insight into the formation of interfacial crud from the interactions between solutes and diluents of the organic phase in solvent extraction.

Synthesis, structural, multitargeted molecular docking analysis of anti-cancer, anti-tubercular, DNA interactions of benzotriazole based macrocyclic ligand

Biologically important macromolecule 1, 1′, 3, 3′ Bis − [2,3,5,6-Tetramethyl-p-phenylenebis(methylene)] dibenzotriazlinium dibromide hydrate (BTD) was synthesized and characterized using FT-IR, NMR and single-crystal XRD (SCXRD). SCXRD revealed that the compound was crystallized as a monoclinic system and associated through weak intermolecular interactions like H-bonding and π- π stacking interactions. These weak intermolecular interactions in BTD were studied using Crystal Explorer and Gaussian. The calculated energies for the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) showed the stability and reactivity of the title compound. Molecular electrostatic potential (MEP) surface analysis was used to investigate the crystal’s nucleophilic and electrophilic reactive sites. The molecular shape and intermolecular interactions in the crystal structure were determined using Hirshfeld surface analysis and fingerprint plots. Anticancer, anti-bacterial and DNA binding ability of BTD were investigated by experimental and theoretical techniques. The obtained results suggest that BTD possesses better anti-cancer, anti-bacterial and DNA binding abilities. The mode of action of antibiotic and anticancer approach was discussed. This provides promising therapeutic advantages for further development.

Graphene Oxide‐Assisted Molecular Crystal Co‐Assembly for Large‐Scale Freestanding 2D Photoresponse Heterostructures with Synaptic Plasticity

Abstract2D van der Waals heterostructures (2D vdWHs) have been gaining significant attention in neuromorphic electronics. However, the facile synthesis of large‐scale, high‐quality freestanding 2D vdWHs remains challenge, particularly for organic counterparts due to susceptible nucleation behaviors and weak intermolecular interactions. Here, the study reports a graphene oxide (GO)‐assisted molecular crystal co‐assembly method for one‐step growth of centimeter‐scale freestanding heterostructures. This co‐assembly involves the simultaneous assembling of organic and GO precursors at the liquid–liquid interface, where the amphiphilic nature of GO nanosheets facilitates the diffusion of organic molecules and 2D nucleation of organic crystals, and the nanosheets also become enriched to grow a quasi‐solid film for the bilayer formation. Owing to integrated photosensitive and charge‐trapping properties as well as type II band structure, this heterostructure exhibits exceptional photonic synaptic behaviors, with a paired‐pulse facilitation index of 141% and image recognition of 91%.

Applicability of self-consistent reaction field (SCRF) method to DFT estimation of hydrogen isotope separation factors in reversible processes

ABSTRACT In earlier quantum chemical calculations of isotope effects, chemical species in the liquid phase were generally treated as existing in the gas phase. In recent years, however, advances in computational programs have made it easier for the self-consistent reaction field (SCRF) method to handle chemical species in the liquid phase, and as a result, it has become easier to apply the SCRF method to isotope effect calculations. This paper concerns the scope of application of the DFT-SCRF method to reversible processes for hydrogen isotope enrichment. It is found that the applicability of the method depends on the type of the intermolecular interaction in the liquid phase and the degree of hydrogen isotope effect (separation factor) on which the process is based. When the magnitude of the isotope effect of the separation system is greater than 10–1, the simple SCRF method is fully applicable; when the magnitude is around 10–2, SCRF with a dimer model, in which the monomer is replaced by a dimer, is applicable for the analysis of the liquid phase with relatively strong intermolecular interactions. Anharmonic correction to the separation factor calculated based on harmonic frequencies may be effective to systems with the liquid phase with weak intermolecular interactions.

Origin of Melt Memory Effects in Poly(ethylene oxide): The Crucial Role of Entanglements.

The melt memory effect on crystallization is an intriguing phenomenon displayed by semicrystalline polymers, as opposed to low molar mass molecules. It concerns the effect of melt temperature on nucleation upon recrystallization. Typically, polymer crystals must be considerably superheated to erase the effect of previous morphology on the subsequent crystallization, avoiding an acceleration of the process. Despite being known for decades, its origin is still not fully understood. Investigating model poly(ethylene oxide) covering a wide range of molar mass, it is demonstrated that melt memory originates from topological constraints among the chains, i.e., entanglements, for PEO in which weak intermolecular interactions are present due to the ether groups. In fact, no memory is observed for samples below the critical molar mass for the formation of entanglements (about 1 kg mol-1). The increase in molar mass raises the number of entanglements and induces the formation of folded chains crystals, both factors leading to a topologically complex amorphous phase, enhancing the melt memory effect. The molecular origin of the melt memory effect in polymers with weak intermolecular interactions is thus ascribed to a slower isotropization in the melt of the chain segments originally contained in the crystals, due to the presence of entanglements among the chains. This study defines the distinction between small molecules and polymers from the point of view of melt memory.

Dicyanopyridine derivatives: One-pot preparation, ACQ-to-AIE transformation, light-conversion quality and photostability

Low cost and strong fluorescence emission are two important guarantees for luminogens used as light conversion agents. By one-pot multicomponent approach and inexpensive starting materials, three dicyanopyridine (DP) derivatives named as DCP (2-amino-6-methoxy-4-phenylpyridine-3,5-dicarbonitrile), DCO (2-amino-6-methoxy-4-(4-methoxyphenyl) pyridine-3,5-dicarbonitrile) and DCC (2-amino-4-(4-cyanophenyl)-6-methoxypyridine-3,5-dicarbonitrile) were designed and synthesized.Meanwhile, the ACQ-to-AIE transformation was successfully realized by altering substituent groups rather than traditional rotor–stator theory. Based on crystal analysis and theoretical calculations, the ACQ-to-AIE transformation is attributed to the tunable stacking modes and intermolecular weak interactions. Owing to matched fluorescence emission, low lost, high yield, and AIE activity, DCC is used as light conversion agents and doped in EVA matrix. The light conversion quality confirms that DCC can not only convert ultraviolet light, but also significantly improve the transmittance of 25 %/40 % EVA, whose photosynthetic photon flux density at 400–500 nm and 600–700 nm increased to 30.67 %/30.21 % and 25.37 %/37.82 % of the blank film, respectively. After 20 h of UV irradiation (365 nm, 40 W), the fluorescence intensities of DCC films can maintain 92 % of the initial values, indicating good photostability in the doping films. This work not only provides an excellent and low-cost light conversion agent, but also has important significance for ACQ-to-AIE transformation of luminogens.

Comparing the crystal structures and spectroscopic properties of a p-hydroxy styrylquinolinium dye with those of its p-dimethylamino analogue

Two previously synthesized styrylquinolinium dyes, namely (E)-1-butyl-4-(4-(dimethylamino)styryl)quinolinium iodide (D36) and (E)-1-butyl-4-(4-hydroxystyryl)quinolinium iodide (D34), were compared in terms of their properties by single-crystal X-ray diffraction (XRD), Hirshfeld surface analysis, Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), fluorescence, and ultraviolet–visible (UV–Vis) spectroscopy, and 1H- and 13C-NMR methods. Both dyes D36 and D34 crystallized in the triclinic and monoclinic systems in the centrosymmetric space groups P-1 and P21/n, respectively. The unit cell of D36 contains two molecules of the dye, participating in weak intermolecular interactions, whereas that of D34 contains four formula units. The phenolic hydroxy group of D34 participates in the formation of a hydrogen bond with the iodide anion. The 4-styrylquinolinium moieties of the cationic dye molecules are nearly planar. The dihedral angle between the mean planes through the ten-membered quinolinium system and the benzene ring is 7.5° in D36 and 5.9(1)° in D34. The structural parameters planarity and bond length alternation (BLA) are discussed, which are important for the evaluation of the first hyperpolarizability β at the molecular level, even in a centrosymmetric crystal. The UV–visible spectra of the dyes in 14 solvents of different polarities were investigated. The reversible solvatochromic behavior of the dyes is demonstrated experimentally and compared with known “binuclear dyes” by evaluating the Rezende model. Dye D36 does not fluoresce, and D34 has a very low emission in the solvents tested.

Novel Trinuclear Copper(II) Complex: Crystal Structure at 100 K and Magnetic Properties of (R, S)-di[(6,7-dimethoxy-isoquinolin-1-yl)-(3,4-dimethoxy-phenyl)-methanolato]-tetra(2-hydroxybenzoato)-diaqua-tricopper dihydrate, [Cu3(C7H5O3)4(C20H20NO5)2(H2O)2]·2(H2O)

The crystal structure of [Cu3(C7H5O3)4(C20H20NO5)2(H2O)2]·2(H2O) (1) and analysis of temperature and field dependence of magnetic susceptibility is reported in this work. The structure of 1 is composed of trinuclear complex units and water molecules. The middle copper atom occupies the center of symmetry. N, O-bonded (6,7-dimethoxy-isoquinolin-1-yl)-(3,4-di­methoxy-phenyl)-methanolato ligands, 2-hydroxybenzoates with bridging carboxylic groups, and oxo-bridged water molecules connect the middle Cu(II) atom with the terminal copper atoms. Two 2-hydroxybenzoates coordinate the terminal copper atoms via one carboxylic oxygen and an O atom of the hydroxyl group. The analysis of copper coordination by bond-valence sum approach and relevant structural correlation is consistent with hexacoordinated Cu(II) centers. Cu···Cu separation is 3.0269(3) Å. The magnetism of 1 shows a strong ferromagnetic interaction between the neighboring metallic centers accompanied by very weak antiferromagnetic intermolecular interactions. The complex units are mutually held by π···π stack interactions of 2-hydroxybenzoates and hydrogen bonds.Graphical A new N,O bonded ligands, (R, S)-[(6,7-dimethoxy-isoquinolin-1-yl)-(3,4-dimethoxy-phenyl)-methanolate] coordinate the terminal atoms of the trinuclear copper(II) complex.

Supramolecular architecture of sodium heterocyclic dithiocarbamate salt: Insights from spectral analysis and bond valence sum characterization

The hydrated sodium salt of 1,2,3,4-tetrahydroquinolinedithiocarbamate (1) has been successfully synthesized and characterized using IR, NMR, and X-ray single crystal analysis. The υC–S and thioureide υC–N bands appeared at 1484 cm−1 and 968 cm−1, respectively, in Na(H2O)3+(thqdtc)– • H2O. The notable NCS2 carbon signal emerged at 212 ppm, credited to unique nitrogen and sulfur-induced deshielding effects. Compound 1 crystallizes in the monoclinic system, P21/c space group, with dimensions a = 14.4297(4) Å, b = 6.1534(2) Å, c = 17.6701(4) Å, β = 108.7340(10)°, V = 1485.83(7) Å3, and Z = 4. The structure of 1 exhibits a supramolecular architecture through secondary interactions, such as weak intermolecular interactions that link the molecules into a linear polymeric chain. The incorporation of heterocyclic rings in the dithiocarbamate ligands leads to the formation of an intriguing supramolecular architecture, as confirmed by BVS analysis results. The BVS value of sodium does not agree well with the formal oxidation state due to the interactions of anions, cations, coordinated and uncoordinated water molecules.

Understanding Emergent Complexity from a Single-Molecule Perspective.

Molecules, with structural, scaling, and interaction diversities, are crucial for the emergence of complex behaviors. Interactions are essential prerequisites for complex systems to exhibit emergent properties that surpass the sum of individual component characteristics. Tracing the origin of complex molecular behaviors from interactions is critical to understanding ensemble emergence, and requires insights at the single-molecule level. Electrical signals from single-molecule junctions enable the observation of individual molecular behaviors, as well as intramolecular and intermolecular interactions. This technique provides a foundation for bottom-up explorations of emergent complexity. This Perspective highlights investigations of various interactions via single-molecule junctions, including intramolecular orbital and weak intermolecular interactions and interactions in chemical reactions. It also provides potential directions for future single-molecule junctions in complex system research.

Quantum chemical calculation for synthesis some thiazolidin-4-one derivatives

In this study, outline the synthesis and spectroscopic characterization of novel 2-imino-thiazolidin-4-one derivatives. The synthesis process is divided into three main parts. Firstly, we prepared the starting material, 2-amino-4-(substitutedphenyl)-1,3-thiazole, by reacting thiourea with substituted acetophenone in the presence of iodine. The second part involved the synthesis of 2-chloroacetamido-4-(substitutedphenyl)-1,3-thiazole through the reaction of heterocyclic amine with chloroacetyl chloride in benzene. The third part focused on the cyclization reaction of synthesized intermediate compounds, leading to the formation of a new series of desired products, namely, 2-imino-3-[4-(substitutedphenyl)-1,3-thiazol-2-yl] thiazolidin-4-ones. The structures of the synthesized compounds were determined based on spectral data, including IR, 1HNMR, and 13CNMR. Various analytical methods were employed to explore intermolecular interactions, nonlinear optical properties, HOMO-LUMO energy gap, potential energy maps, Natural Bond Orbital (NBO) analysis, and thermodynamic parameters of diverse compounds. The assessment of weak intermolecular interactions using Noncovalent interactions (NCI) and reduced density gradient (RDG) methods revealed the presence of robust hydrogen bonds, van der Waals forces, and steric effects within the compounds. Topological parameters highlighted significant hydrogen bonding capabilities among the studied compounds. Additionally, the analysis of the HOMO-LUMO energy gap and other quantum chemical parameters unveiled the influence of protonation on polarization, chemical reactivity, and corrosion resistance. Molecular Electrostatic Potential (MEP) analysis indicated changes in electrophilicity and nucleophilicity upon the addition of protons, altering chemical reactivity. Stabilization energies of donor-acceptor interactions, assessed through Natural Bond Orbital (NBO) analysis, provided insights into charge transfer and conjugative interactions, particularly emphasizing electron delocalization within the compounds' phenyl rings.

Molecular Electronics: From Nanostructure Assembly to Device Integration.

Integrated electronics and optoelectronics based on organic semiconductors have attracted considerable interest in displays, photovoltaics, and biosensing owing to their designable electronic properties, solution processability, and flexibility. Miniaturization and integration of devices are growing trends in molecular electronics and optoelectronics for practical applications, which requires large-scale and versatile assembly strategies for patterning organic micro/nano-structures with simultaneously long-range order, pure orientation, and high resolution. Although various integration methods have been developed in past decades, molecular electronics still needs a versatile platform to avoid defects and disorders due to weak intermolecular interactions in organic materials. In this perspective, a roadmap of organic integration technologies in recent three decades is provided to review the history of molecular electronics. First, we highlight the importance of long-range-ordered molecular packing for achieving exotic electronic and photophysical properties. Second, we classify the strategies for large-scale integration of molecular electronics through the control of nucleation and crystallographic orientation, and evaluate them based on factors of resolution, crystallinity, orientation, scalability, and versatility. Third, we discuss the multifunctional devices and integrated circuits based on organic field-effect transistors (OFETs) and photodetectors. Finally, we explore future research directions and outlines the need for further development of molecular electronics, including assembly of doped organic semiconductors and heterostructures, biological interfaces in molecular electronics and integrated organic logics based on complementary FETs.

Paxillin phase separation promotes focal adhesion assembly and integrin signaling.

Focal adhesions (FAs) are transmembrane protein assemblies mediating cell-matrix connection. Although protein liquid-liquid phase separation (LLPS) has been tied to the organization and dynamics of FAs, the underlying mechanisms remain unclear. Here, we experimentally tune the LLPS of PXN/Paxillin, an essential scaffold protein of FAs, by utilizing a light-inducible Cry2 system in different cell types. In addition to nucleating FA components, light-triggered PXN LLPS potently activates integrin signaling and subsequently accelerates cell spreading. In contrast to the homotypic interaction-driven LLPS of PXN in vitro, PXN condensates in cells are associated with the plasma membrane and modulated by actomyosin contraction and client proteins of FAs. Interestingly, non-specific weak intermolecular interactions synergize with specific molecular interactions to mediate the multicomponent condensation of PXN and are efficient in promoting FA assembly and integrin signaling. Thus, our data establish an active role of the PXN phase transition into a condensed membrane-associated compartment in promoting the assembly/maturation of FAs.

Naphthalene Diimide-Based Metallacage as an Artificial Ion Channel for Chloride Ion Transport.

Developing synthetic molecular devices for controlling ion transmembrane transport is a promising research field in supramolecular chemistry. These artificial ion channels provide models to study ion channel diseases and have huge potential for therapeutic applications. Compared with self-assembled ion channels constructed by intermolecular weak interactions between smaller molecules or cyclic compounds, metallacage-based ion channels have well-defined structures and can exist as single components in the phospholipid bilayer. A naphthalene diimide-based artificial chloride ion channel is constructed through efficient subcomponent self-assembly and its selective ion transport activity in large unilamellar vesicles and the planar lipid bilayer membrane by fluorescence and ion-current measurements is investigated. Molecular dynamics simulations and density functional theory calculations show that the metallacage spans the entire phospholipid bilayer as an unimolecular ion transport channel. This channel transports chloride ions across the cell membrane, which disturbs the ion balance of cancer cells and inhibits the growth of cancer cells at low concentrations.

Study of PEG-b-PLA/Eudragit S100 Blends on the Nanoencapsulation of Indigo Carmine Dye and Application in Controlled Release.

A nanocapsule shell of poly(ethylene glycol)-block-poly(d,l-lactic acid) (PEG-b-PLA) mixed with anionic Eudragit S100 (90/10% w/w) was previously used to entrap and define the self-assembly of indigo carmine (IC) within the hydrophilic cavity core. In the present work, binary blends were prepared by solution mixing at different PEG-b-PLA/Eudragit S100 ratios (namely, 100/0, 90/10, 75/25, and 50/50% w/w) to elucidate the role of the capsule shell in tuning the encapsulation of the anionic dye (i.e., IC). The results showed that the higher content of Eudragit S100 in the blend decreases the miscibility of the two polymers due to weak intermolecular interactions between PEG-b-PLA and Eudragit S100. Moreover, with an increase in the amount of Eudragit S100, a higher thermal stability was observed related to the mobility restriction of PEG-b-PLA chains imposed by Eudragit S100. Formulations containing 10 and 25% Eudragit S100 exhibited an optimal interplay of properties between the negative surface charge and the miscibility of the polymer blend. Therefore, the anionic character of the encapsulating agent provides sufficient accumulation of IC molecules in the nanocapsule core, leading to dye aggregates following the self-assembly. At the same time, the blending of the two polymers tunes the IC release properties in the initial stage, achieving slow and controlled release. These findings give important insights into the rational design of polymeric nanosystems containing organic dyes for biomedical applications.