Noncovalent Intermolecular Interactions Research Articles

Fabrication and Encapsulation of Soy Peptide Nanoparticles Using Ultrasound Followed by Spray Drying.

Peptide aggregation inevitably occurs during hydrolysis, and insoluble peptide aggregates (ISPA) are used as feed for animals due to their poor water solubility and unpleasant bitter flavor. Ultrasound was used to fabricate soy peptide nanoparticles by reassembling ISPA, followed by spray-drying encapsulation to develop low-bitterness peptide microcapsules with soluble soybean polysaccharide (SSPS) and stevioside (STE) as wall materials. Powder properties, bitter taste, and the morphology of the microcapsules were evaluated. The formation of soluble peptide nanoparticles (<200 nm) was observed after ultrasound due to the reassembly of ISPA through the disruption of non-covalent intermolecular interactions. A gradual reduction in bitter taste was observed with increasing ultrasonic time. Moreover, spray-drying encapsulation with STE could effectively improve the flowability and wettability of the microcapsule powder owing to the rapid migration of surface-active STE to the atomized droplet surface, as evidenced by the lower angle of repose and wettability time. Peptide microcapsules with STE (spherical particles with smooth surfaces) exhibited lower density and reduced bitterness because STE (0-0.1%, w/w) exhibited an excellent bitter-masking effect. With high STE concentrations (>0.5%, w/w), microcapsules exhibited a higher bitter taste than unencapsulated peptides due to the increased surface distribution of STE on the microcapsules. These results provide an effective technique to improve the physicochemical properties of ISPA.

Computational Insights for Interactions between nsP2 and nsP3 of CHIKV and Hormones through DFT Computations and Molecular Dynamics Simulations.

The non-structural protein (nsP2 & nsP3) of the Chikungunya virus (CHIKV) is responsible for the transmission of viral infection. The main role of non-structural proteins are involved in the transcription process at an early stage of the infection. In this work, authors have studied the impact of nsP2 and nsP3 of CHIKV on hormones present in the human body using a computational approach. The ten hormones of chemical properties such as 4-Androsterone-2,17-dione, aldosterone, androsterone, corticosterone, cortisol, cortisone, estradiol, estrone, progesterone and testosterone were taken as a potency. From the molecular docking, the binding energy of the complexes is estimated, and cortisone was found to be the highest negative binding energy (-6.57 kcal/mol) with the nsP2 and corticosterone with the nsP3 (-6.47 kcal/mol). This is based on the interactions between hormones and nsP2/nsP3, which are types of noncovalent intermolecular interactions categorized into three types: electrostatic interactions, van der Waals (vdW) interactions, and hydrogen-bonding (H-bonding) interactions. To validate the docking results, additional molecular dynamics simulations and MM-GBSA methods were performed. The change in enthalpy, entropy, and free energy were calculated using MM-GBSA methods. The nsP2 and nsP3 of CHIKV interact strongly with the cortisone and corticosterone with free energy changes of -20.55 & -36.08 kcal/mol, respectively. Methods: The crystal structures of 3TKR and 3GPO proteins of nsP2 and nsP3 were extracted from the RCSB Protein Data Bank. Initially, unnecessary atoms like extra cations or anions and missing explicit hydrogen atoms were removed and added from the native domain of nsP2 and nsP3. The alignment of coordinated in the native domain was performed using Chimera and Notepad++ tools. The molecular docking of protein and ligand was performed usingAutoDock tool; it is essential for the prediction of the orientation of the ligand into the cavity of the target protein based on binding affinity. Based on thermodynamic parameters, MD Simulations were employed to calculate the change in binding free energies of various complexes followed by a change in enthalpy and entropy with time. According to MD production, the CPPTAJ and PTRAJ programs were used to analyse the trajectories, such as dynamic stability (RMSD), residual fluctuation (RMSF), compatibility, and hydrogen bonds of the newly formed complexes. After that, the Density Functional Theory (DFT) were used to calculate the electronic properties of selected molecules by Gaussian 16 on applying the B3LYP method with the 6-311G (d, p) basis set.

Synthesis and Electrochemical Properties of Organic Gel Electrolytes Based on Low Molecular Weight Gelators

Introduction Several low molecular weight organic gelators (LMOGs) which are able to produce thermo-reversible gels (i.e., physical gels) with organic solvents have been discovered, and the gels are of great attentions for their application to organic gel electrolytes of Li-ion battery, dye-sensitized solar cells and so on [1]. These molecules create fibrous aggregates by self-assembly through non-covalent intermolecular interactions then they trap the solution, resulting in gelation.In our previous papers, LMOG having perfluoroalkyl groups in the molecules can gelate aprotic polar solvents such as propylene carbonate (PC), γ-butyrolactone (GBL) and so on [2]. However, the correlation between LMOGs and the electrochemical properties of gel electrolytes formed using them has not been elucidated.Here, we report preparation of LMOGs and thermal and electrochemical properties of the Li-ion gel electrolytes. Experimental Preparation of gels and determination of the sol-gel temperatures are as follows: Weighed amounts of a liquid and LMOG were placed into a glass tube (10 mmφ). The tubes were heated until all solid material had dissolved and then cooled. The transition temperatures were determined by the inverse flow method.Linear sweep voltammetry (LSV) measurements for Li-ion electrolyte solution and the gel electrolyte were carried out in a potential range of 0–7 V vs Li/Li+ (≈ -3–4 V vs Ag/Ag+) at a rate of 1.0 mV s-1, where a pair of platinum were used as working and counter electrodes, and a silver wire was used as a reference then the potential converted to the appropriate values. The electrolyte solution was a 1M LiPF6/the mixture of ethylene carbonate and ethyl methyl carbonate (EC:EMC = 1:2 and/or 3:7). Cyclic voltammetry (CV) was carried out in a potential range of 0–3 V vs Li/Li at a rate of 1.0 mV s-1, where natural spheroidal graphite purchased from Hosen Co. Ltd. was used as a working electrode, and a pair of lithium metals were used as counter and reference electrodes. Results and Discussion The sol-gel transition temperature for gel electrolyte was found to be a function of the concentration of LMOG, where the concentration of LMOG increases, the transition temperature also increases. The transition temperatures also depend on the chemical structure of the LMOG and were approximately 30 ºC to 50 ºC at a concentration of about 5% of LMOG.The results of LSV measurements of the Li-ion electrolyte and the gel electrolyte prepared by the addition of LMOG were very similar, indicating that the LMOG shows high electrochemical stability. The CV results indicate that the presence of the LMOG in the electrolyte solution is similar to the neat electrolyte solution on cycling behavior.In this presentation, the preparation of the LMOGs, and thermal and electrochemical properties of the gel electrolyte will be discussed in terms of the chemical structure of the LMOGs. Acknowledgements This work is financially supported by JST SPRING [JPMJSP2111] and YAMAGUCHI UNIVERSITY FUND (to K.M.), JSPS KAKENHI [22H03781, 23K25035], Paloma environmental technology development foundation, Hoso Bunka Foundation, Japan Keirin Autorace Foundation and Iketani Science and Technology Foundation (to H.O.). Reference [1] L. Tao, et al., J. Mater. Chem. A, 3, 2344 (2015).[2] T. Yoshida, et al., Bull. Chem. Soc. Jpn, 88, 1447 (2015), A. Ohashi, et al., Chem. Lett., 47, 810 (2018). Figure 1

Efficiency Enhancement in Peptide Hydrogelators: The Crucial Role of Side Chain Hydrogen Bonding Over Aromatic π-π Interactions.

Short peptide assemblies that form supramolecular hydrogels are stabilized by both intermolecular noncovalent interactions among amino acid side chains and hydrogen bonding between peptide backbone amides. Previous research has emphasized the inclusion of aromatic amino acids in short peptide sequences, positing that aromatic π-π interactions contribute significantly to inducing efficient hydrogelation i.e., at low minimum gelation concentrations (MGCs). However, herein, we demonstrate that additional hydrogen bonding interactions from amino acid side chains play a more pivotal role in the efficiency of peptide hydrogelation compared to aromatic π-π interactions. We investigated two sets of Fluorenylmethoxycarbonyl (Fmoc)-functionalized α-synuclein and human islet amyloid peptide fragments [Fmoc-NVGGAVVT (Syn-N) and Fmoc-NFGAIL (IAP-N)], substituting asparagine (N) with phenylalanine (Syn-F/IAP-F), alanine (Syn-A/IAP-A), and glutamine (Syn-Q/IAP-Q). This allowed us to explore the effects of aromatic (π-system), aliphatic (hydrophobic), and hydrogen bonding effects with varying chain lengths on hydrogel formation. Our results reveal that Syn-N and Syn-Q exhibit MGC of 0.03 and 0.05 wt %, respectively, classifying them as super hydrogelators (MGC < 0.1 wt %). These values are 4.0-6.6-fold lower than Syn-F and Syn-A, with Syn-N demonstrating greater efficiency than Syn-Q. Similarly, IAP-N exhibited a substantial decrease in MGC by 8.75, 3.75, and 2.5 folds compared to IAP-A, IAP-F, and IAP-Q, respectively. Experimental evidence and molecular dynamic simulation suggest that -CO-NH2 of asparagine side chains effectively engaged in hydrogen bonding, thereby immobilizing water molecules at low gelator concentrations. Although glutamine shares similar -CO-NH2 functionality, its hydrogelation efficiency is less pronounced compared to asparagine, likely due to its longer alkyl chain, which may hinder the formation of a hydrogen bonding network in the self-assembled structure compared to asparagine-containing peptides. These findings offer valuable insights for designing efficient peptide hydrogelators or lowering MGCs by substituting amino acids with asparagine/glutamine in peptide sequences. Additionally, modifying peptide properties through asparagine/glutamine substitution could optimize hydrogel properties for specific applications.

The synergistic immunomodulatory activity of Lycium barbarum glycopeptide and isochlorogenic acid A on RAW264.7 cells.

Regulation of the immune system to maintain homeostasis in the organism has become a focus of research, and the synergistic effect of multi-component complexes will effectively improve the immunomodulatory activity. The present study aimed to investigate the interaction and synergistic immunomodulatory activity of isochlorogenic acid A (IAA) and Lycium barbarum glycopeptide (LbGp). The results obtained indicated that non-covalent intermolecular interactions were employed to form the LbGp-IAA complex, with a binding ratio of 135.15 mg g-1. The formation of LbGp-IAA complex altered the conformation of LbGp, and IAA was mainly bound to LbGp by van der Waals forces and hydrogen bonds. In addition, LbGp-IAA promoted the proliferation of RAW264.7 cells. The IAA and LbGp interaction had a synergistic effect on the promotion of phagocytosis and the expression of nitric oxide, tumor necrosis faction-α and interleukin-1β, which improved the immunomodulatory effect of LbGp. Furthermore, the combination of LbGp and IAA synergistically inhibited lipopolysaccharide-induced inflammatory response. In summary, the binding of IAA enhanced the immunomodulatory activity of LbGp and coordinated the immune response, and did not trigger an inflammatory response, which was potentially attributed to the alteration of spatial structure of LbGp through the binding of IAA. The results provide new perspectives for the study of glycopeptide-polyphenol interactions. © 2024 Society of Chemical Industry.

Glucoconjugated Dinuclear Copper(II) Complex: An Efficient Catalyst for Stereoselective Synthesis of Trisubstituted Propargylamines via Solvent-free A3 Coupling Reaction.

Development of catalytic systems using nontoxic natural precursors is the need of the era, and along this line, we have synthesized a new D-glucose derived ligand (4,6-O-ethylidene-N-(2-hydroxy-4-(octyloxy)benzylidene)-β-D-glucopyranosylamine) and its dinuclear copper(II) complex. The molecular structure of the complex has been established by single-crystal X-ray diffraction studies and detailed noncovalent intermolecular interactions present in it have been explored by Hirshfeld surface analysis. Further, the complex has been used as a catalyst in the enantioselective (87-99 % ee) synthesis of propargylamines in good to excellent yield (82-95 %) via aldehyde-amines-alkynes (A3) coupling reaction under solvent-free condition. The formation of aminal intermediate during the reaction has been confirmed by 1H-NMR and single-crystal X-ray diffraction studies. The catalytic system is reusable without any appreciable loss in the enantioselectivity or product yield.

Supradecoration induced novel Properties: A comparative study of Ferrocene and Ferrocenyl α-aminophosphonate

Decorating chemical motifs with appropriate functional groups capable of supramolecular interactions hold key in modulating these novel systems for targeted applications. This work by means of a comparative study of Ferrocene and Ferrocenyl α- aminophosphonate highlight supradecoration induced multi paradigm properties across materials to medicine. The observed results indicate an increase in crystal framework energy with induction of mechanochromism and aggregation-induced emission in case of Ferrocenyl-α-amino phosphonate as novel supra decorated Ferrocene motif. Comparative BSA and BLC studies indicated improved biocompatibility with enhancement of catalase enzyme activity in case of Ferrocenyl-α- aminophosphonate compared to pristine Ferrocene. The relative quantification of intermolecular non covalent interactions of Ferrocene and Ferrocenyl-α- aminophosphonate evaluated using Quantum crystallographic methods and non-covalent interaction analysis were used to corroborate the supramodulation effects. The observed influence of Ferrocenyl α-aminophosphonate on the enzymatic activity of catalase was also examined using a comparative molecular docking analysis. The docking results corroborated influence of supradecoration on binding affinity and binding site, which are vital for designing ligands of enhanced catalase activity and also helpful in prediction of newer regulatory sites on enzyme. Taken together this work signifies how supra decoration of Ferrocene motif with functionalities capable of diverse intermolecular non-covalent interactions modulate molecular properties for newer applications.

Crystallographic Studies on Non-Covalent Interactions in Aryl-Substituted Antimony Organometallics

A series of novel and previously published organoantimony compounds (RnSbX3−n, X = Cl, Br; R = o-tolyl, 2,6-xylyl, 1-naphthyl, and 9-anthracenyl), were synthesized and characterized. In addition, single-crystal X-ray diffraction was employed to elucidate the molecular structures of all solid species. These compounds display non-covalent intermolecular interactions in the form of edge-to-face, π···π stacking, and CH3···π interactions, and the effects of the substituent type and substituent bulk on the nature of these interactions present will be highlighted and discussed.

Quantitative evaluation of noncovalent interactions with negative fragmentation approach including basis set superposition error correction

Abstract We propose a negative fragmentation approach (NFA), including counterpoise (CP) correction to basis set superposition error (BSSE) for quantitatively evaluating intra- and intermolecular noncovalent interactions. Noncovalent interactions are widely found in chemistry and biology and are regarded as essential interactions. However, there are few general methods for evaluating these individual intra- and intermolecular interaction energies because of two issues: (i) difficulty in the evaluation of intramolecular interactions due to the interacting sites connected with covalent bonds and (ii) BSSE affecting the quantitative accuracy of interaction analysis. In our scheme, we overcome the issue (i) using the NFA scheme, which can evaluate intra- and intermolecular interactions as a fragment–fragment interaction of interacting sites, and address the issue (ii) using the CP method. Here, NFA including the CP correction was applied to various molecular systems, providing comparable results for intermolecular interactions to supermolecule calculations with the CP correction and also succeeding in the evaluation of intramolecular interactions and its BSSEs. It is notable that our NFA scheme does not require any particular program or a modification of the program codes. These indicate that many researchers can apply our NFA scheme to various molecular systems.

A zero-dimensional 1-butylpiperazine-cadmium(II) hybrid material: Synthesis, structural analysis, and DFT studies

This study reports the synthesis and characterization of an organoammonium-cadmium(II) hybrid material, (BPH₂)₂[Cd₂Cl₈] (BP = 1-butylpiperazine), using a combination of experimental and theoretical techniques. Single-crystal X-ray diffraction shows a centrosymmetric crystal structure in the P1¯ space group, featuring a zero-dimensional (0D) arrangement where binuclear [Cd₂Cl₈]⁴⁻ anions and (C₈H₂₀N₂⁺) cations are linked by N—H···Cl and C—H···Cl hydrogen bonds. Hirshfeld surface analysis further elucidates these intermolecular noncovalent interactions, highlighting the dominant role of H···Cl contacts in the molecular packing. The crystal morphology is further investigated via the Bravais-Friedel-Donnay-Harker (BFDH) model. Infrared (IR) spectroscopic analysis was conducted to identify vibrational modes, confirm structure, and elucidate bonding features. Additionally, Experimental UV–visible study indicates an optical band gap energy of 4.75 eV, and density functional theory (DFT) calculations corroborate these findings, predicting a direct band gap of 4.45 eV. Moreover, theoretical calculations, including the complex dielectric function, band structure, and total density of states (DOS), were performed to explore the electrical and optical properties. Finally, the chemical reactivity was evaluated using conceptual-DFT descriptors at the B3LYP/SDD/aug-cc-pVTZ level of theory.

Triadic Halobenzene Processing Additive Combined Advantages of Both Solvent and Solid Types for Efficient and Stable Organic Solar Cells.

Solvent additives with a high boiling point (BP) and low vapor pressure (VP) have formed a key handle for improving the performance of organic solar cells (OSCs). However, it is not always clear whether they remain in the active-layer film after deposition, which can negatively affect the reproducibility and stability of OSCs. In this study, an easily removable solvent additive (4-chloro-2-fluoroiodobenzene (CFIB)) with a low BP and high VP is introduced, behaving like volatile solid additives that can be completely removed during the device fabrication process. In-depth studies of CFIB addition into the D18-Cl donor and N3 acceptor validate its dominant non-covalent intermolecular interactions with N3 through effective electrostatic interactions. Such phenomena improve charge dynamics and kinetics by optimizing the morphology, leading to enhanced performance of D18-Cl:N3-based devices with a power conversion efficiency of 18.54%. The CFIB-treated device exhibits exceptional thermal stability (T80 lifetime = 120h) at 85°C compared with the CFIB-free device, because of its morphological robustness by evolving no residual CFIB in the film. The CFIB features a combination of advantages of solvent (easy application) and solid (high volatility) additives, demonstrating its great potential use in the commercial mass production of OSCs.

Synthesis, structural characterization, molecular docking analysis and Carbonic Anhydrase IX inhibitory evaluations of novel Cerium(III)-based MOF constructed from 1,10-phenanthroline and fumaric acid.

In this study, a novel Cerium-based MOFs with 1,10-phenanthroline (phen) and fumaric acid (H2fum) has been hydrothermally synthesized as single crystal structurally characterized by X-ray diffraction, IR spectroscopy and ATG measurements. This compound corresponds to the formula: [Ce2(phen)2(fum)3(H2O)2]n(I), it crystallizes in the triclinic system with space group P1¯, with the following parameters: a = 9.062(1) Å, b = 10.0608(5) Å, c = 10.603(1) Å, α = 72.545(6) °, β = 77.57(1) °, γ = 69.959(6) °, V = 859.49(14) Å3, Z = 2.The structure revealed 2D bridged polymeric chains where the adjacent Ce(III) atoms are bridged by fumarate linkers with a mean intermetallic distance of about 9.36 Å. H···O bonds link the 2D sheets leading to a pseudo 3D network, while the stability of the structure is assured by a weak π-π stacking between parallel and opposed phen ligands.The Ce3+ cation is nona-coordinated and it is in a distorted tricapped trigonal prism geometry.Hirshfeld surface analysis was used to investigate the non-covalent intermolecular interactions and the dominant H···O, H···C and H···H contacts were quantified. The thermal properties of the considered coordination polymer (I) are also discussed and disclose that (I) is stable up to 300°C. Besides, this study explores the potential of (I) as an inhibitor of the carbonic anhydrase IX enzyme (CA IX), a critical player in tumor microenvironment regulation. Through molecular docking simulations, we elucidate the binding interactions between (I) and CA IX, the results suggest the efficiency of (I) as a CA IX inhibitor. Moreover, we assessed the drug-likeness properties and ADMET characteristics of (I), providing valuable insights for its potential as a therapeutic agent.

Quantification of CH and NH/π-Stacking Interactions in Cells Using Nuclear Magnetic Resonance Spectroscopy.

π-Stacking, a type of noncovalent interactions involving aromatic residues, plays an important role in protein folding and function. In this work, an attempt has been made to measure CH/π and NH/π stacking interactions in a protein in Escherichia coli cells using a combined double-mutant cycle and nuclear magnetic resonance spectroscopy method. The results show that the CH/π and NH/π stacking interactions are generally weaker in cells than those in the buffer. The transient intermolecular noncovalent interactions between the protein and the complex cellular environment may compete with and thus weaken the stacking interactions in the protein. The weakening of stacking interactions can enhance the local conformational opening of proteins in E. coli cells. This is evident from the faster rates of amide hydrogen/deuterium exchange observed in cells than in the buffer, for residues that undergo local conformational opening. This study highlights the influence of the cellular environment on π-stacking and the conformational dynamics of proteins.

Nanoparticles of nucleotide-free analogue of vitamin B12 formed in protein nanocarriers and their neuroprotective activity in vivo

Recently, we have described the first supermolecular nanoentities of vitamin B12 derivative, viz. monocyano form of heptabutyl cobyrinate, unique nanoparticles with strong noncovalent intermolecular interactions, emerging optical and catalytic properties. Their nearest analogue, heptamethyl cobyrinate (ACCby), exhibits bioactivity. Here, we demonstrate the first example of the formation of nanoparticles of this nucleotide-free analogue of vitamin B12 in protein nanocarriers and neuroprotective activity in vivo of the own nanoform of the drug. The preparation and characterization of nanocarriers based on bovine serum albumin (BSA) loaded with vitamin B12 (viz. cyano- and aquacobalamins) and ACCby were performed. Nucleotide-free analogue of vitamin B12 is tightly retained by the protein structure and exists in an incorporated state in the form of nanoparticles. The effect of encapsulated drugs on the character and severity of primary generalized seizures in rats induced by the pharmacotoxicant thiosemicarbazide was studied. Cyanocobalamin and ACCby exhibited a neuroprotective effect. The best influence of the encapsulation on the effectiveness of the drugs was achieved in the case of AСCby, whose bioavailability as a neuroprotector did not change upon introduction in BSA particles, i.e., 33 % of surviving animals were observed upon ACCby administration in free form and in encapsulated state. No surviving rats were observed without the administration of drugs. Thus, BSA nanocarriers loaded by nanoparticles of nucleotide-free analogues of vitamin B12, including hydrophobic ones, can be recommended for neuroprotection and targeted delivery.

An Energetic and Topological Approach to Understanding the Interplay of Noncovalent Interactions in a Series of Crystalline Spiropyrrolizine Compounds.

Synthesis of quinoline-containing spiropyrrolizine was achieved via a 1,3-dipolar cycloaddition reaction of azomethine ylide (generated in situ from ninhydrin and l-proline) and (E)-2-styrylquinoline. The synthesized compounds were characterized by 1H NMR, 13C NMR, HRMS, and single-crystal XRD analysis. The XRD data revealed that the solid-state structures of the compounds belong to the monoclinic system of the space group P21/c and are stabilized through various weak noncovalent interactions such as C-H···O, C-H···π, and π···π interactions. The noncovalent interactions are characterized and quantified through Hirshfeld surface analysis. Moreover, the interaction energies of the intermolecular noncovalent interactions are calculated through PIXEL calculation. The PIXEL calculation provides precise interaction energy with an energy decomposition scheme. Energy Framework calculations have also been performed to delve deeper into understanding the intermolecular interactions. The intermolecular interactions are further characterized using Bader's theory of "atoms in molecules" (QTAIM) and the "noncovalent" (NCI) interaction plot index. The nature and strength of noncovalent interactions are analyzed from the topological parameters at (3, -1) bond critical points (BCPs).

Guanidinium and spermidinium decavanadates: as small biomimetic models to understand non-covalent interactions between decavanadate and arginine and lysine side chains in proteins

During the last three decades, numerous investigations have been conducted on polyoxidovanadates to treat several illnesses and inhibit enzymes. Numerous decavanadate compounds have been proposed as potential therapies for Diabetes mellitus, Cancer, and Alzheimer’s disease. Only six relevant functional proteins interacting with decavanadate, V10, have been deposited in the PDB. These are acid phosphatase, tyrosine kinase, two ecto-nucleoside triphosphate diphosphohydrolases (NTPDases), the human transient receptor potential cation channel (TRPM4), and the human cell cycle protein CksHs1. The interaction sites in these proteins mainly consist of Arginine and Lysine, side chains binding to the decavanadate anion. To get further knowledge regarding non-covalent interactions of decavanadate in protein environments, guanidinium and spermidinium decavanadates were synthesized, crystallized, and subjected to analysis utilizing various techniques, including FTIR, Raman, 51V-NMR, TGA, and X-ray diffraction. The DFT calculations were employed to calculate the interaction energy between the decavanadate anion and the organic counterions. Furthermore, the Quantum Theory of Atoms in Molecules (QTAIM) and Non-covalent Interaction-Reduced Density Gradient (NCI-RDG) analyses were conducted to understand the non-covalent interactions present in these adducts. Decavanadate can engage in electrostatic forces, van der Waals, and hydrogen bond interactions with guanidinium and spermidinium, as shown by their respective interaction energies. Both compounds were highly stabilized by strong hydrogen bond interactions N−H···O and weak non-covalent interactions C−H···O. In addition, the interactions between guanidinium and spermidinium cations and decavanadate anion form several stable rings. This study provides new information on non-covalent intermolecular interactions between decavanadate and small biomimetic models of arginine and lysine lateral chains in protein environments.

A bioinspired supramolecular nanoprodrug for precision therapy of B-cell non-Hodgkin’s lymphoma

Fludarabine (FA) is still considered as a first-line chemotherapy drug for hematological tumors related to B lymphocytes. However, it is worth noting that the non-specific distribution and non-different cytotoxicity of FA may lead to irreversible consequences such as central nervous system damage such as blindness, coma, and even death. Therefore, it is very important to develop a system to targeting delivery FA. In preliminary studies, it was found that B lymphoma cells would specific highly expressing the sialic acid-binding immunoglobulin-like lectin 2 (known as CD22). Inspired by the specific recognition of sialic acid residues and CD22, we have developed a supramolecular prodrug based on polysialic acid, an endogenous biomacromolecule, achieving targeted-therapy of B-cell non-Hodgkin’s lymphoma (B-NHL). Specifically, the prepared hydrophobic reactive oxygen species-responsive FA dimeric prodrug (F2A) interacts with the TPSA, which polysialic acid were modified by the thymidine derivatives, through non-covalent intermolecular interactions similar to “Watson–Crick” base pairing, resulting in the formation of nanoscale supramolecular prodrug (F@TPSA). Cell experiments have confirmed that F@TPSA can be endocytosed by CD22+ B lymphoma cells including Raji and Ramos cells, and there is a significant difference of endocytosis in other leukocytes. Furthermore, in B-NHL mouse model, compared with FA, F@TPSA is determined to have a stronger tumor targeting and inhibitory effect. More importantly, the distribution of F@TPSA in vivo tends to be enriched in lymphoma tissue rather than nonspecific, thus reducing the leukopenia of FA. The targeted delivery system based on PSA provides a new prodrug modification strategy for targeted treatment of B-NHL.Graphical abstract

Crystalline Porous Organic Cage Membranes Constructed Using Fortified Intermolecular Interactions for Molecular Sieving.

Among the various types of materials with intrinsic porosity, porous organic cages (POCs) are distinctive as discrete molecules that possess intrinsic cavities and extrinsic channels capable of facilitating molecular sieving. However, the fabrication of POC membranes remains highly challenging due to the weak noncovalent intermolecular interactions and most reported POCs are powders. In this study, we constructed crystalline free-standing porous organic cage membranes by fortifying intermolecular interactions through the induction of intramolecular hydrogen bonds, which was confirmed by single-crystal X-ray analysis. To elucidate the driving forces behind, a series of terephthaldehyde building blocks containing different substitutions were reacted with flexible triamine under different conditions via interfacial polymerization (IP). Furthermore, density functional theory (DFT) calculations suggest that intramolecular hydrogen bonding can significantly boost the intermolecular interactions. The resulting membranes exhibited fast solvent permeance and high rejection of dyes not only in water, but also in organic solvents. In addition, the membrane demonstrated excellent performance in precise molecular sieving in organic solvents. This work opens an avenue to designing and fabricating free-standing membranes composed of porous organic materials for efficient molecular sieving.

Crystalline Porous Organic Cage Membranes Constructed Using Fortified Intermolecular Interactions for Molecular Sieving

AbstractAmong the various types of materials with intrinsic porosity, porous organic cages (POCs) are distinctive as discrete molecules that possess intrinsic cavities and extrinsic channels capable of facilitating molecular sieving. However, the fabrication of POC membranes remains highly challenging due to the weak noncovalent intermolecular interactions and most reported POCs are powders. In this study, we constructed crystalline free‐standing porous organic cage membranes by fortifying intermolecular interactions through the induction of intramolecular hydrogen bonds, which was confirmed by single‐crystal X‐ray analysis. To elucidate the driving forces behind, a series of terephthaldehyde building blocks containing different substitutions were reacted with flexible triamine under different conditions via interfacial polymerization (IP). Furthermore, density functional theory (DFT) calculations suggest that intramolecular hydrogen bonding can significantly boost the intermolecular interactions. The resulting membranes exhibited fast solvent permeance and high rejection of dyes not only in water, but also in organic solvents. In addition, the membrane demonstrated excellent performance in precise molecular sieving in organic solvents. This work opens an avenue to designing and fabricating free‐standing membranes composed of porous organic materials for efficient molecular sieving.

An Innovative Vortex-Assisted Liquid-Liquid Microextraction Approach Using Deep Eutectic Solvent: Application for the Spectrofluorometric Determination of Rhodamine B in Water, Food and Cosmetic Samples.

A new green and highly sensitive method for the determination of rhodamine B (RhB) by deep eutectic solvent-based vortex-assisted liquid-liquid microextraction with fluorescence detection (DES-VALLME-FLD) was developed. The extraction efficiency of conventional solvents and different deep eutectic solvent (DES) systems composed of tetrabutylammonium bromide (TBAB) and an alcohol (hexanol, octanol, or decanol) in different ratios were compared. DFT calculations of intermolecular electrostatic and non-covalent interactions of the most stable RhB forms with DES and water explain the experimental DESs' extraction efficiency. Semiempirical PM7 computations were used to obtain Hansen solubility parameters, which supported the good solubility of the monocationic RhB form in selected DESs. The dependence of the linear calibration of microextraction into 100 µL DES was observed in the RhB calibration range from 0.2 to 10.0 µg L-1 with a correlation coefficient of R2 = 0.9991. The LOD value was calculated to be 0.023 µg L-1. The accuracy and precision of the proposed method were verified over two days with RSD values of 2.9 to 4.1% and recovery of 94.6 to 103.7%. The developed method was applied to the determination of RhB in real samples (tap water, energy drink, and lipstick).